Macromolecular Corrosion (McIn) Inhibitors: Structures, Methods Of Making And Using The Same

ABSTRACT

methods of producing compounds represented by structural formula (I) and their use in inhibiting corrosion in corrodible material.

RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application No.62/465,666, filed on Mar. 1, 2017. The entire teachings of the aboveapplication are incorporated herein by reference.

GOVERNMENT SUPPORT

This invention was made with government support under IIP-1632258 fromthe National Science Foundation. The government has certain rights inthe invention.

FIELD OF INVENTION

This invention relates newly developed multifunctional environmentallyfriendly macromolecular corrosion inhibitors utilize mainly therenewable and biobased raw material source. Most of the currentcorrosion inhibitors used in the industrial applications are notnecessarily environmentally friendly and are based on petroleum basedchemicals involving organic and inorganic species.

BACKGROUND OF THE INVENTION

This invention is directed to multifunctional macromolecular corrosioninhibitors and to fluid compositions containing minor amounts thereof.Multifunctional properties of this inhibitor include but not limited torust inhibition, copper corrosion inhibition, and water and oilseparating (demulsifier) capabilities. Fluids include but not limited tolubricants, biolubricants, bio-oils, bio-based oils, syntheticlubricants, fuels, bio-fuel, greases, bio-greases, aviation fuels,kerosene, gasoline, diesel, biodiesel, adhesives, and paints etc.

Corrosion in general terms is the degradation of a material caused by anaggressive environment such as water, air (oxygen), chemicals (acids,bases), organic liquids, oil, and gas, etc. Materials subject tocorrosion include metals and their alloys, plastics, paints andcoatings, concrete, or composites. Corrosion is a major concern in thedurability of these materials, impacting safety, causing environmentaldamage, and incurring enormous repair and replacement costs. This is amajor national concern. According to one United States federalgovernment study in 2002, the total estimated cost of corrosion is astaggering $276 billion (approximately 3.1% of GDP) (ReportFHWA-RD-01-156). If indirect costs are included, this increases to 6% ofGDP ($552 billion), because of loss of productivity, delays, materialfailures, etc. It does not appear that newer studies exist. The directeffects of metal corrosion are (a) loss of mechanical strength andstructural failure, (b) perforation of fluid transmission pipes, storagetanks, and ships, leading to leakage of harmful fluids into theenvironment, (c) contamination of fluid due to leaching of metal speciesfrom vessels' inner surfaces, (d) mechanical damage causing failure ofstructures, engines, pumps, and valves, and (e) events hazardous tohuman life due to excessive structural failure. Corrosion inhibitorsplay a key role in mitigating some of these corrosion issues. Corrosioninhibitors are typically added or treated (0.001% to 5%) to thecorroding materials (metals, lubricants, fuels, plastics, oils and gas,adhesives, greases, paints and coating materials, cement, waterreservoir, etc.) to protect against the corrosion from the surroundingenvironments like fluid, water, oxygen, moisture, weather, temperature,or their combinations, etc.

Environmental risks associated with corrosion inhibitors are forcing toseek more environmentally friendly products. Some products are alsoincreasingly subject to restrictions by government agencies in the USAand other countries. These harmful substances can enter the environmentdirectly when formulated fluids like lubricants come in contact withwater, soil, or 50 air, via leakage or spillage from industrialequipment, ships, automobiles, engines, earth-moving equipment,drilling, metal working fluids, hydropower plants, hydraulics andturbines (wind, water, steam, aviation), transformers, chain saw, gears,elevators, wire and ropes, two-stroke engines, etc. Corrosion inhibitorsare added to fluids based on petroleum, synthetic and/or bio-oils,bio-based oils like lubricants, greases, adhesives, and fuels; andpaints and coating 55 materials. Thus, there is need to replace harmfulcompounds with environmentally-friendly and sustainable corrosioninhibitors without sacrificing performance. The present invention is anew material composition technology, Macromolecular Corrosion Inhibitors(McIn), described herein. McIn is envisioned as a disruptive technologythat adds value to the supply chains of multiple market sectors.

BRIEF SUMMARY OF THE INVENTION

This invention is essentially directed to macromolecular corrosioninhibitors that are

-   -   (a) the composition of polymers which are the reaction products        of the starting materials comprising a substituted phenol and an        aldehyde that is esterified further with an alkyl acid through        oxalyl chloride or thionyl chloride or alkyl acids and using        catalysts, if required to accelerate the esterification process,    -   (b) the composition of polymers which are the reaction products        of the starting materials comprising a substituted phenol and an        aldehyde and are further reacted with an alkenyl succinic        anhydride to form a half ester products having free carboxylic        acid groups in the repeating units,    -   (c) the composition of polymers which are the reaction products        of the starting materials comprising a substituted phenol and an        aldehyde and are further reacted with alkylene oxides (e.g.        propylene oxide) to form phenol-derived alcohols in the        repeating units,    -   (d) the composition of polymers that are the reaction products        of the starting materials of a substituted phenol and an        aldehyde which are esterified further with oleic acid and then        reacted with a maleic anhydride to form succinic anhydride        adduct, and finally reacted with an alkyl alcohol to form a half        ester product having free carboxylic acid groups in the        repeating units,    -   (e) the composition of reaction products derived from a maleic        anhydride and an oleate which are the condensation products of        oleic acid and alkyl alcohol that are further reacted with alkyl        alcohol to form a half ester product having free carboxylic acid        groups,    -   (f) the composition of reaction products derived from a maleic        anhydride and a substituted phenol-oleate further reacted with        an alkyl alcohol to form a half ester product having free        carboxylic acid groups. Substituted phenol-oleate is the        condensation product of oleic acid and a substituted phenol,    -   (g) the composition of reaction products of the starting        materials comprising a substituted phenol and an alkylene oxides        (e.g. propylene oxide) is further reacted with an alkenyl        succinic anhydride to form a half ester product having free        carboxylic acid groups, or    -   (h) the composition of polymers which are the reaction products        of the starting materials comprising a substituted phenol and an        aldehyde and are further reacted with alkylene oxides (e.g.        propylene oxide) to form phenol-derived alcohols in the        repeating units, is further reacted with an alkenyl succinic        anhydride to form a half ester product having free carboxylic        acid groups,    -   (i) the composition of polymers that are the reaction products        of a substituted phenol and an aldehyde which are reacted with        an alkylene oxide (e.g. propylene oxide) and then esterified        further with an oleic acid and then reacted with a maleic        anhydride to form succinic anhydride adduct, and finally reacted        with an alkyl alcohol to form a half ester product having free        carboxylic acid groups in the repeating units.

The present invention pertains to a compound represented by structuralformula I and IA:

-   -   wherein:    -   X is:

-   -   each R₁ is H, independently an optionally substituted C₁-C₂₀        alkyl group, an optionally substituted C₁-C₁₀ alkyl group, a        tertiary carbon group, a methyl group, a methoxy group, an        optionally substituted aryl group, and optionally substituted        alkoxy group, an optionally substituted carbonyl group, an        optionally substituted alkoxycarbonyl group, an        optionally-CH(R′″)(R′″COOH) wherein each R′″ independently        C₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an        optionally substituted carbocyclic or heterocyclic non-aromatic        ring;    -   i=0, 1, 2, 3;    -   j=0 or 1;    -   n is an integer from 1 to 1000, or an integer from 1 to 100, or        an integer from 1 to 50, or an integer from 1 to 25, or an        integer from 1 to 15, or preferably an integer from 1 to 10;    -   when n=1, then j=0;    -   when n>1 then j=1;    -   each R₂ and R₃ is independently H, a C1-C8 linear or branched or        cyclic alkyl chain, an optionally substituted C₁-C₂₀ alkyl        group, an optionally substituted C₁-C₁₀ alkyl group, a tertiary        carbon group, a methyl group, a methoxy group, an optionally        substituted aryl group, and optionally substituted alkoxy group,        an optionally substituted carbonyl group, an optionally        substituted alkoxycarbonyl group, or —CH(R′″)(R′″COOH);    -   R is a C₁-C₂₄ linear or branched alkyl chain, alkenyl chain, or        an isomerized structure or a mixture of isomerized (A) and (B):

-   -   wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain,        when n is 1 and j is 0,    -   R in Structure I is a mixture of isomerized structures of

and

-   -   R^(d) is a C1-C24 linear or branched alkyl chain

DETAILED DESCRIPTION OF THE INVENTION Definitions

For convenience, before further description of the present invention,certain terms employed in the specification, examples and appendedclaims are collected here. These definitions should be read in light ofthe remainder of the disclosure and understood as by a person of skillin the art. Unless defined otherwise, all technical and scientific termsused herein have the same meaning as commonly understood by a person ofordinary skill in the art.

The articles “a” and “an” are used herein to refer to one or to morethan one (i.e. to at least one) of the grammatical object of thearticle. By way of example, “an element” means one element or more thanone element.

The terms “comprise” and “comprising” are used in the inclusive, opensense, meaning that additional elements may be included.

The term “including” is used herein to mean “including but not limitedto”. “Including” and “including but not limited to” are usedinterchangeably.

The term “polymer” is art-recognized and refers to a macromoleculecomprising a repeating monomeric unit. The number of repeat units mayvary as low as 2 and as high as million. In the present invention thisnumber may vary from 2 to about 10,000, or less than 1,000, or less thanabout 100, or even less than about 10.

The term “monomer” is art-recognized and refers to a compound that isable to combine in long chains with other like or unlike molecules toproduce.

The terms “number average molecular weight”, or “Mn”, “weight averagemolecular weight”, “Z-average molecular weight” and “viscosity averagemolecular weight” are art-recognized. When the term “molecular weight”or an exemplary molecular weight is described herein, the measure ofmolecular weight will be clear from the context and/or will include allapplicable measures.

“Small molecule” is an art-recognized term. In certain embodiments, thisterm refers to a molecule which has a molecular weight of less thanabout 2000 amu, or less than about 1000 amu, and even less than about200 amu.

The term “aliphatic” is an art-recognized term and includes linear,branched, and cyclic alkanes, alkenes, or alkynes. In certainembodiments, aliphatic groups in the present invention are linear orbranched and have from 1 to about 30 carbon atoms.

The term “alkyl” is art-recognized and includes saturated aliphaticgroups, including straight-chain alkyl groups, branched-chain alkylgroups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkylgroups, and cycloalkyl substituted alkyl groups. In certain embodiments,a straight chain or branched chain alkyl has about 30 or fewer carbonatoms in its backbone (e.g., C₁-C₃₀ for straight chain, C₃-C₃₀ forbranched chain), and alternatively, about 20 or fewer. Likewise,cycloalkyls have from about 3 to about 10 carbon atoms in their ringstructure, and alternatively about 5, 6 or 7 carbons in the ringstructure. The term “alkyl” is also defined to include halosubstitutedalkyls.

The term “aralkyl” is art-recognized, and includes alkyl groupssubstituted with an aryl group (e.g., an aromatic or heteroaromaticgroup).

The terms “alkenyl” and “alkynyl” are art-recognized, and includeunsaturated aliphatic groups analogous in length and possiblesubstitution to the alkyls described above, but that contain at leastone double or triple bond respectively.

Unless the number of carbons is otherwise specified, “lower alkyl”refers to an alkyl group, as defined above, but having from one to tencarbons, alternatively from one to about six carbon atoms in itsbackbone structure. Likewise, “lower alkenyl” and “lower alkynyl” havesimilar chain lengths.

The term “heteroatom” means nitrogen, oxygen, or sulfur and includes anyoxidized form of nitrogen and sulfur and the quaternized form of anybasic nitrogen. Also, the term “nitrogen” includes substitutablenitrogen of a heteroaryl or non-aromatic heterocyclic group. As anexample, in a saturated or partially unsaturated ring having 0-3heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen maybe N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR″ (asin N-substituted pyrrolidinyl), wherein R″ is a suitable substituent forthe nitrogen atom in the ring of a non-aromatic nitrogen-containingheterocyclic group.

The term “aryl” is art-recognized, and includes 5-, 6- and 7-memberedsingle-ring aromatic groups that may include from zero to fourheteroatoms, for example, benzene, pyrrole, furan, thiophene, imidazole,oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazineand pyrimidine, and the like. Those aryl groups having heteroatoms inthe ring structure may also be referred to as “aryl heterocycles”“heteroaryls,” or “heteroaromatics.” The aromatic ring may besubstituted at one or more ring positions with such substituents asdescribed above, for example, halogen, azide, alkyl, aralkyl, alkenyl,alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino,amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether,alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl,aromatic or heteroaromatic moieties, —CF₃, —CN, or the like. The term“aryl” also includes polycyclic ring systems having two or more cyclicrings in which two or more carbons are common to two adjoining rings(the rings are “fused rings”) wherein at least one of the rings isaromatic, e.g., the other cyclic rings may be cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls. The termsortho, meta and para are art-recognized and apply to 1, 2-, 1, 3- and 1,4-disubstituted benzenes, respectively. For example, the names 1,2-dimethylbenzene and ortho-dimethylbenzene are synonymous.

The terms “heterocyclyl” and “heterocyclic group” are art-recognized,and include 3- to about 10-membered ring structures, such as 3- to about7-membered rings, whose ring structures include one to four heteroatoms.Heterocycles may also be polycycles. Heterocyclyl groups include, forexample, thiophene, thianthrene, furan, pyran, isobenzofuran, chromene,xanthene, phenoxathiin, pyrrole, imidazole, pyrazole, isothiazole,isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine,isoindole, indole, indazole, purine, quinolizine, isoquinoline,quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline,cinnoline, pteridine, carbazole, carboline, phenanthridine, acridine,pyrimidine, phenanthroline, phenazine, phenarsazine, phenothiazine,furazan, phenoxazine, pyrrolidine, oxolane, thiolane, oxazole,piperidine, piperazine, morpholine, lactones, lactams such asazetidinones and pyrrolidinones, sultams, sultones, and the like. Theheterocyclic ring may be substituted at one or more positions with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

The terms “polycyclyl” and “polycyclic group” are art-recognized, andinclude structures with two or more rings (e.g., cycloalkyls,cycloalkenyls, cycloalkynyls, aryls and/or heterocyclyls) in which twoor more carbons are common to two adjoining rings, e.g., the rings are“fused rings”. Rings that are joined through non-adjacent atoms, e.g.,three or more atoms are common to both rings, are termed “bridged”rings. Each of the rings of the polycycle may be substituted with suchsubstituents as described above, as for example, halogen, alkyl,aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, amino, nitro,sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl,silyl, ether, alkylthio, sulfonyl, ketone, aldehyde, ester, aheterocyclyl, an aromatic or heteroaromatic moiety, —CF₃, —CN, or thelike.

The term “carbocycle” is art recognized and includes an aromatic ornon-aromatic ring in which each atom of the ring is carbon. The flowingart-recognized terms have the following meanings: “nitro” means —NO₂;the term “halogen” designates —F, —Cl, —Br or —I; the term “sulfhydryl”means —SH; the term “hydroxyl” means —OH; and the term “sulfonyl” means—SO₂ ⁻.

The terms “amine” and “amino” are art-recognized and include bothunsubstituted and substituted amines, e.g., a moiety that may berepresented by the general formulas:

wherein R50, R51 and R52 each independently represent a hydrogen, analkyl, an alkenyl, —(CH₂)_(m)—R61, or R50 and R51, taken together withthe N atom to which they are attached complete a heterocycle having from4 to 8 atoms in the ring structure; R61 represents an aryl, acycloalkyl, a cycloalkenyl, a heterocycle or a polycycle; and m is zeroor an integer in the range of 1 to 8. In certain embodiments, only oneof R50 or R51 may be a carbonyl, e.g., R50, R51 and the nitrogentogether do not form an imide. In other embodiments, R50 and R51 (andoptionally R52) each independently represent a hydrogen, an alkyl, analkenyl, or —(CH₂)_(m)—R61. Thus, the term “alkylamine” includes anamine group, as defined above, having a substituted or unsubstitutedalkyl attached thereto, i.e., at least one of R50 and R51 is an alkylgroup.

The term “acylamino” is art-recognized and includes a moiety that may berepresented by the general formula:

wherein R50 is as defined above, and R54 represents a hydrogen, analkyl, an alkenyl or —(CH₂)_(m)—R61, where m and R61 are as definedabove.

The term “amido” is art recognized as an amino-substituted carbonyl andincludes a moiety that may be represented by the general formula:

wherein R50 and R51 are as defined above. Certain embodiments of theamide in the present invention will not include imides which may beunstable.

The term “alkylthio” is art recognized and includes an alkyl group, asdefined above, having a sulfur radical attached thereto. In certainembodiments, the “alkylthio” moiety is represented by one of —S-alkyl,—S-alkenyl, —S-alkynyl, and —S—(CH₂)_(m)—R61, wherein m and R61 aredefined above. Representative alkylthio groups include methylthio, ethylthio, and the like.

The term “carbonyl” is art recognized and includes such moieties as maybe represented by the general formulas:

wherein X50 is a bond or represents an oxygen or a sulfur, and R55represents a hydrogen, an alkyl, an alkenyl, —(CH₂)_(m)—R61 or apharmaceutically acceptable salt, R56 represents a hydrogen, an alkyl,an alkenyl or —(CH₂)_(m)—R61, where m and R61 are defined above. WhereX50 is oxygen and R55 or R56 is not hydrogen, the formula represents an“ester”. Where X50 is oxygen, and R55 is as defined above, the moiety isreferred to herein as a carboxyl group, and particularly when R55 ishydrogen, the formula represents a “carboxylic acid”. Where X50 is anoxygen, and R56 is hydrogen, the formula represents a “formate”. Ingeneral, where the oxygen atom of the above formula is replaced bysulfur, the formula represents a “thiocarbonyl” group. Where X50 is asulfur and R55 or R56 is not hydrogen, the formula represents a“thioester.” Where X50 is a sulfur and R55 is hydrogen, the formularepresents a “thiocarboxylic acid.” Where X50 is a sulfur and R56 ishydrogen, the formula represents a “thioformate.” On the other hand,where X50 is a bond, and R55 is not hydrogen, the above formularepresents a “ketone” group. Where X50 is a bond, and R55 is hydrogen,the above formula represents an “aldehyde” group.

The terms “alkoxyl” or “alkoxy” are art recognized and include an alkylgroup, as defined above, having an oxygen radical attached thereto.Representative alkoxyl groups include methoxy, ethoxy, propyloxy,tert-butoxy and the like. An “ether” is two hydrocarbons covalentlylinked by an oxygen. Accordingly, the substituent of an alkyl thatrenders that alkyl an ether is or resembles an alkoxyl, such as may berepresented by one of —O-alkyl, —O-alkenyl, —O-alkynyl,—O—(CH₂)_(m)—R61, where m and R61 are described above.

The term “sulfonate” is art recognized and includes a moiety that may berepresented by the general formula:

in which R57 is an electron pair, hydrogen, alkyl, cycloalkyl, or aryl.

The term “sulfate” is art recognized and includes a moiety that may berepresented by the general formula:

in which R57 is as defined above.

The term “sulfonamido” is art recognized and includes a moiety that maybe represented by the general formula:

in which R50 and R56 are as defined above.

The term “sulfamoyl” is art-recognized and includes a moiety that may berepresented by the general formula:

in which R50 and R51 are as defined above.

The term “sulfonyl” is art recognized and includes a moiety that may berepresented by the general formula:

in which R58 is one of the following: hydrogen, alkyl, alkenyl, alkynyl,cycloalkyl, heterocyclyl, aryl or heteroaryl.

The term “sulfoxido” is art recognized and includes a moiety that may berepresented by the general formula:

in which R58 is defined above.

The term “phosphoramidite” is art recognized and includes moietiesrepresented by the general formulas:

wherein Q51, R50, R51, and R59 are as defined above.

The term “phosphonamidite” is art recognized and includes moietiesrepresented by the general formulas:

wherein Q51, R50, R51, and R59 are as defined above, and R60 representsa lower alkyl or an aryl.

As used herein the term non-aromatic carbocyclic ring as used alone oras part of a larger moiety refers to a non-aromatic carbon containingring which can be saturated or unsaturated having three to fourteenatoms including monocyclic and polycyclic rings in which the carbocyclicring can be fused to one or more non-aromatic carbocyclic orheterocyclic rings or one or more aromatic (carbocyclic or heterocyclic)rings.

An optionally substituted aryl group as defined herein may contain oneor more substitutable ring atoms, such as carbon or nitrogen ring atoms.Examples of suitable substituents on a substitutable ring carbon atom ofan aryl group include halogen (e.g., —Br, Cl, I and F), —OH, C1-C4alkyl, C1-C4 haloalkyl, —NO₂, C1-C4 alkoxy, C1-C4 haloalkoxy, —CN, —NH₂,C1-C4 alkylamino, C1-C4 dialkylamino, —C(O)NH₂, —C(O)NH(C1-C4 alkyl),—C(O)(C1-C4 alkyl), —OC(O)(C1-C4 alkyl), —OC(O)(aryl),—OC(O)(substituted aryl), —OC(O)(aralkyl), —OC(O)(substituted aralkyl),—NHC(O)H, —NHC(O)(C1-C4 alkyl), —C(O)N(C1-C4 alkyl)₂, —NHC(O)O—(C1-C4alkyl), —C(O)OH, —C(O)O—(C1-C4 alkyl), —NHC(O)NH₂, —NHC(O)NH(C1-C4alkyl), —NHC(O)N(C1-C4 alkyl)₂, —NH—C(═NH)NH₂,—SO₂NH₂—SO₂NH(C1-C3alkyl), —SO₂N(C1-C3alkyl)₂, NHSO₂H, NHSO₂(C1-C4alkyl) and optionally substituted aryl. Preferred substituents on arylgroups are as defined throughout the specification. In certainembodiments aryl groups are unsubstituted.

Examples of suitable substituents on a substitutable ring nitrogen atomof an aryl group include C1-C4 alkyl, NH₂, C1-C4 alkylamino, C1-C4dialkylamino, —C(O)NH₂, —C(O)NH(C1-C4 alkyl), —C(O)(C1-C4 alkyl),—CO₂R**, —C(O)C(O)R**, —C(O)CH₃, —C(O)OH, —C(O)O—(C1-C4 alkyl),—SO₂NH₂—SO₂NH(C1-C3 alkyl), —SO₂N(C1-C3 alkyl)₂, NHSO₂H, NHSO₂(C1-C4alkyl), —C(═S)NH₂, —C(═S)NH(C1-C4 alkyl), —C(═S)N(C1-C4 alkyl)₂,—C(═NH)—N(H)₂, —C(═NH)—NH(C1-C4 alkyl) and —C(═NH)—N(C1-C4 alkyl)₂,

An optionally substituted alkyl group or non-aromatic carbocyclic orheterocyclic group as defined herein may contain one or moresubstituents. Examples of suitable substituents for an alkyl groupinclude those listed above for a substitutable carbon of an aryl and thefollowing: ═O, ═S, ═NNHR**, ═NN(R**)₂, ═NNHC(O)R**, ═NNHCO₂ (alkyl),═NNHSO₂ (alkyl), ═NR**, spiro cycloalkyl group or fused cycloalkylgroup. R** in each occurrence independently is —H or C1-C6 alkyl.Preferred substituents on alkyl groups are as defined throughout thespecification. In certain embodiments optionally substituted alkylgroups are unsubstituted.

A “spiro cycloalkyl” group is a cycloalkyl group which shares one ringcarbon atom with a carbon atom in an alkylene group or alkyl group,wherein the carbon atom being shared in the alkyl group is not aterminal carbon atom.

Analogous substitutions may be made to alkenyl and alkynyl groups toproduce, for example, aminoalkenyls, aminoalkynyls, amidoalkenyls,amidoalkynyls, iminoalkenyls, iminoalkynyls, thioalkenyls, thioalkynyls,carbonyl-substituted alkenyls or alkynyls.

The definition of each expression, e.g. alkyl, m, n, etc., when itoccurs more than once in any structure, is intended to be independent ofits definition elsewhere in the same structure unless otherwiseindicated expressly or by the context.

The term “selenoalkyl” is art recognized and includes an alkyl grouphaving a substituted seleno group attached thereto. Exemplary“selenoethers” which may be substituted on the alkyl are selected fromone of —Se-alkyl, —Se-alkenyl, —Se-alkynyl, and —Se—(CH₂)_(m)—R61, m,and R61 are defined above.

The terms triflyl, tosyl, mesyl, and nonaflyl are art-recognized andrefer to trifluoromethanesulfonyl, p-toluenesulfonyl, methanesulfonyl,and nonafluorobutanesulfonyl groups, respectively. The terms triflate,tosylate, mesylate, and nonaflate are art-recognized and refer to atrifluoromethanesulfonate ester, p-toluenesulfonate ester,methanesulfonate ester, and nonafluorobutanesulfonate ester functionalgroups and molecules that contain said groups, respectively.

The abbreviations Me, Et, Ph, Tf, Nf, Ts, and Ms are art recognized andrepresent methyl, ethyl, phenyl, trifluoromethanesulfonyl,nonafluorobutanesulfonyl, p-toluenesulfonyl and methanesulfonyl,respectively. A more comprehensive list of the abbreviations utilized byorganic chemists of ordinary skill in the art appears in the first issueof each volume of the Journal of Organic Chemistry; this list istypically presented in a table entitled Standard List of Abbreviations.

The abbreviations OSA is for octenyl succinic anhydride, DDSA is fordodecenyl succinic anhydride, ODSA is for octadecenyl succinicanhydride, and PIBSA is for polyisobutylene succinic anhydridepreferably with low molecular weights (300-1500 molecular weight), andOASA is for oleic acid succinic anhydride.

The term an isomer is understood a molecule with the same molecularformula as another molecule, but with a different chemical structure.Isomers contain the same number of atoms of each element but havedifferent arrangements of their atoms. Isomers do not necessarily sharesimilar properties unless they also have the same functional groups. Instructural isomers, sometimes referred to as constitutional isomers, theatoms, and functional groups are joined together in different ways. Thechain isomers whereby hydrocarbon chains have variable amounts ofbranching; position isomers, which deals with the position of afunctional group on a chain; and functional group isomerism, in whichone functional group is split up into different ones. All such isomers,as well as mixtures thereof, are intended to be included in thisinvention.

Certain monomeric subunits of the present invention may exist inparticular geometric or stereoisomeric forms. In addition, and othercompositions of the present invention may also be optically active. Thepresent invention contemplates all such compounds, including cis- andtrans-isomers, R- and S-enantiomers, diastereomers, (D)-isomers,(L)-isomers, the racemic mixtures thereof, and other mixtures thereof,as falling within the scope of the invention. Additional asymmetriccarbon atoms may be present in a substituent such as an alkyl group. Allsuch isomers, as well as mixtures thereof, are intended to be includedin this invention.

If, for instance, a particular enantiomer of a compound of the presentinvention is desired, it may be prepared by asymmetric synthesis, or byderivation with a chiral auxiliary, where the resulting diastereomericmixture is separated and the auxiliary group cleaved to provide the puredesired enantiomers. Alternatively, where the molecule contains a basicfunctional group, such as amino, or an acidic functional group, such ascarboxyl, diastereomeric salts are formed with an appropriate opticallyactive acid or base, followed by resolution of the diastereomers thusformed by fractional crystallization or chromatographic means well knownin the art, and subsequent recovery of the pure enantiomers.

It will be understood that “substitution” or “substituted with” includesthe implicit proviso that such substitution is in accordance withpermitted valence of the substituted atom and the substituent, and thatthe substitution results in a stable compound, e.g., which does notspontaneously undergo transformation such as by rearrangement,cyclization, elimination, or other reaction.

The term “substituted” is also contemplated to include all permissiblesubstituents of organic compounds. In a broad aspect, the permissiblesubstituents include acyclic and cyclic, branched and unbranched,carbocyclic and heterocyclic, aromatic and nonaromatic substituents oforganic compounds. Illustrative substituents include, for example, thosedescribed herein above. The permissible substituents may be one or moreand the same or different for appropriate organic compounds. Forpurposes of this invention, the heteroatoms such as nitrogen may havehydrogen substituents and/or any permissible substituents of organiccompounds described herein which satisfy the valences of theheteroatoms. This invention is not intended to be limited in any mannerby the permissible substituents of organic compounds.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover. Theterm “hydrocarbon” is art recognized and includes all permissiblecompounds having at least one hydrogen and one carbon atom. For example,permissible hydrocarbons include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds that may be substituted or unsubstituted.

The phrase “protecting group” is art recognized and includes temporarysubstituents that protect a potentially reactive functional group fromundesired chemical transformations. Examples of such protecting groupsinclude esters of carboxylic acids, silyl ethers of alcohols, andacetals and ketals of aldehydes and ketones, respectively. The field ofprotecting group chemistry has been reviewed. Greene et al., ProtectiveGroups in Organic Synthesis 2^(nd) ed., Wiley, New York, (1991).

The phrase “hydroxyl-protecting group” is art recognized and includesthose groups intended to protect a hydroxyl group against undesirablereactions during synthetic procedures and includes, for example, benzylor other suitable esters or ethers groups known in the art.

The term “electron-withdrawing group” is recognized in the art anddenotes the tendency of a substituent to attract valence electrons fromneighboring atoms, i.e., the substituent is electronegative with respectto neighboring atoms. A quantification of the level ofelectron-withdrawing capability is given by the Hammett sigma (σ)constant. This well known constant is described in many references, forinstance, March, Advanced Organic Chemistry 251-59, McGraw Hill BookCompany, New York, (1977). The Hammett constant values are generallynegative for electron donating groups (σ(P)=−0.66 for NH₂) and positivefor electron withdrawing groups (σ(P)=0.78 for a nitro group), σ(P)indicating para substitution. Exemplary electron-withdrawing groupsinclude nitro, acyl, formyl, sulfonyl, trifluoromethyl, cyano, chloride,and the like. Exemplary electron-donating groups include amino, methoxy,and the like.

Contemplated equivalents of the or oligomers, subunits and othercompositions described above include such materials which otherwisecorrespond thereto, and which have the same general properties thereof,wherein one or more simple variations of substituents are made which donot adversely affect the efficacy of such molecule to achieve itsintended purpose of the present invention. In general, the methods ofthe present invention may be methods illustrated in the general reactionschemes as, for example, described below, or by modifications thereof,using readily available starting materials, reagents and conventionalsynthesis procedures. In these reactions, it is also possible to makeuse of variants which are in themselves known but are not mentionedhere.

The present invention pertains to a compound represented by structuralformula I:

-   -   wherein:    -   X is:

-   -   Each R₁ is H, independently an optionally substituted C₁-C₂₀        alkyl group, an optionally substituted C₁-C₁₀ alkyl group, a        tertiary carbon group, a methyl group, a methoxy group, an        optionally substituted aryl group, and optionally substituted        alkoxy group, an optionally substituted carbonyl group, an        optionally substituted alkoxycarbonyl group, an        optionally-CH(R′″)(R′″COOH) wherein each R′″ independently        C₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an        optionally substituted carbocyclic or heterocyclic non-aromatic        ring;    -   i=0, 1, 2, 3;    -   j=0 or 1;    -   n is an integer from 1 to 1000, or an integer from 1 to 100, or        an integer from 1 to 50, or an integer from 1 to 25, or an        integer from 1 to 15, or preferably an integer from 1 to 10;    -   when n=1, then j=0;    -   when n>1 then j=1;    -   each R₂ and R₃ is independently H, a C1-C8 linear or branched or        cyclic alkyl chain, an optionally substituted C₁-C₂₀ alkyl        group, an optionally substituted C₁-C₁₀ alkyl group, a tertiary        carbon group, a methyl group, a methoxy group, an optionally        substituted aryl group, and optionally substituted alkoxy group,        an optionally substituted carbonyl group, an optionally        substituted alkoxycarbonyl group, or —CH(R′″)(R′″COOH);    -   R is a C₁-C₂₄ linear or branched alkyl chain, alkenyl chain, or        an isomerized structure or a mixture of isomerized (A) and (B):

-   -   wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain.

In another embodiment, the present invention addresses that relate to acompound of Structure I wherein

-   -   n=1;    -   j=0;    -   R is a mixture of isomerized structures of

and

-   -   R^(d) is a C₁-C₂₄ linear or branched alkyl chain

In another embodiment, the present invention addresses that relate to acompound represented by structural formula II derived from StructuralFormula I.

Each R₁ is H, independently an optionally substituted C₁-C₂₀ linear orbranched alkyl group, a tertiary carbon group, a methyl group, a methoxygroup, an optionally substituted aryl group, and an optionallysubstituted C₁-C₂₀ linear or branched alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted C₁-C₂₀ linear orbranched alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) whereineach R′″ independently is C₁-C₁₀ linear or branched alkyl chain, —OH,—SH or —NH₂ or an optionally substituted carbocyclic or heterocyclicC₁-C₁₂ non-aromatic ring.

i=0 or 1 or 2 or 3;j=0 or 1;n is an integer from 1 to 1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15,or preferably 0 to 10,when n=1, then j is always 0;when n>1 then j is 1;Each R₂, R₃, R₄ independently is H, methyl, or a C₁-C₂₄ linear orbranched or cyclic alkyl chain.Each R₂, R₃, R₄ is H, independently an optionally substituted C₁-C₂₄alkyl group, an optionally substituted C₁-C₁₀ alkyl group, a tertiarycarbon group, a methyl group, a methoxy group, an optionally substitutedaryl group, and optionally substituted C₁-C₂₀ alkoxy group, anoptionally substituted C₁-C₂₀ carbonyl group, an optionally substitutedC₁-C₂₀ alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) wherein eachR′″ independently C₁-C₁₀ linear or branched alkyl chain, —OH, —SH or—NH₂ or an optionally substituted carbocyclic or heterocyclic C₁-C₁₂non-aromatic ring.R is a C₁-C₂₄ linear or branched alkyl chain, C₁-C₂₄ alkenyl chain or

wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain.

In yet another embodiment of the present invention is a compound ofStructure II wherein each R₂, R₃ is independently an optionally a methylgroup or H; independently an optionally a C₁-C₈ linear, branched, acyclic alkyl group or H.

In another embodiment of the present invention is a compound representedby the Structural Formula III:

wherein, R is a linear or branched C₁-C₂₆ alkyl chain,Each R₁ is H, independently an optionally substituted C₁-C₂₀ linear orbranched alkyl group, a tertiary carbon group, a methyl group, a methoxygroup, an optionally substituted aryl group, and an optionallysubstituted C₁-C₂₀ linear or branched alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted C₁-C₂₀ linear orbranched alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) whereineach R′″ independently is C₁-C₁₀ linear or branched alkyl chain, —OH,—SH or —NH₂ or an optionally substituted carbocyclic or heterocyclicC₁-C₁₂ non-aromatic ring, andi is 0, 1, 2 or 3,n is an integer from 1 to 1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15,or preferably 0 to 10

In another embodiment of the present invention is a compound ofstructural formula (III) where R is a saturated fatty acid derived fromnatural resources like plants, vegetable oils or animal fats.

In another embodiment of the present invention is a compound ofstructural formula (III) where R is a saturated fatty acid, caprylicacid (8:0), capric acid (10:0), lauric acid (12:0), myristic acid(14:0), palmitic acid (16:0), stearic acid (18:0), arachidic acid(20:0), behenic acid (22:0), lignoceric acid (24:0), or ceroticacid(26:0).

In another embodiment of the present invention is a compound ofstructural formula (III) where R is a mixture of saturated alkyl chainsof saturated fatty acids derived natural resources like plants,vegetable oils or animal fat.

In another embodiment, the present invention is a compound of structuralformula (III) where R₁ independently for each occurrence is selectedfrom the group consisting of

In another embodiment, the present invention is a compound of structuralformula (III) where R is represented by

or a mixture of structural isomers.

In another embodiment the present invention is a compound of structuralformula (III) where R is a C₁-C₂₆ linear or branched alkyl chain or amixture of C₈-C₂₄ linear or branched alkyl chains, i is an integer from0 to 3, and R₁ independently for each occurrence is selected from thegroup consisting of

In certain embodiments of the present invention the compounds arerepresented by the following structural formulas:

wherein n is an integer from 0 to 100 or 0 to 50 or 0 to 25, 0 to 15, orpreferably 0 to 10

In another embodiment of the present invention is a compound ofstructural formula (IV-a):

or a mixture of structural isomers.wherein R is a C₁-C₂₆ linear or branched alkyl chain or an alkyl chainof saturated fatty acids derived from renewable resources like plantoils like Jatropha, vegetable oils like canola oil, palm oil, vegetableoils like canola, rapeseed oil, soy oil, palms oil, and alike, andanimal fats like tallow oil. The saturated fatty acids are, caprylicacid (8:0), capric acid (10:0), lauric acid (12:0), myristic acid(14:0), palmitic acid (16:0), stearic acid (18:0), arachidic acid(20:0), behenic acid (22:0), lignoceric acid (24:0), or ceroticacid(26:0).

Each R₁ is H, independently an optionally substituted C₁-C₂₀ linear orbranched alkyl group, a tertiary carbon group, a methyl group, a methoxygroup, an optionally substituted aryl group, and an optionallysubstituted C₁-C₂₀ linear or branched alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted C₁-C₂₀ linear orbranched alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) whereineach R′″ independently is C₁-C₁₀ linear or branched alkyl chain, —OH,—SH or —NH₂ or an optionally substituted carbocyclic or heterocyclicC₁-C₁₂ non-aromatic ring.

i=0 or 1,n is an integer from 0 to 100 or 0 to 50 or 0 to 25, 0 to 15, orpreferably 0 to 10.

In yet another embodiment, the present invention is a compound or amixture of compounds represented by Structural formula III, IV or IVawherein the compound is the composition of that are the reactionproducts of a substituted phenol and an aldehyde which are esterifiedfurther with a linear or branched alkyl alcohol containing a C₁-C₅₀linear or branched alkyl chain or a mixture of C₁-C₅₀ linear or branchedalkyl chains or preferably linear C₁-C₂₆ linear or branched alkyl chainor a mixture of linear or branched C₁-C₂₆ alkyl chains or morepreferably C₁₂-C₁₈ lineal alkyl chain or a mixture of C₁₂-C₁₈ alkylchains.

In another embodiment of the present invention is a compound ofstructural formula V:

wherein R is a C₁-C₂₆ linear or branched alkyl chain or a mixture ofC₈-C₂₄ alkyl chains, i is an integer from >1 but ≤3, and each R₁independently is selected from the group consisting of

In yet another embodiment, the present invention is a compound or amixture of compounds represented by structural formulas VI:

In another embodiment of the present invention represented by structuralformulas IV-V where in R is a C₁-C₂₆ linear or branched alkyl chain or asaturated fatty acid or mixture of saturated fatty acids derived fromrenewable resources like plant oils like Jatropha, vegetable oils likecanola oil, palm oil, vegetable oils like canola, rapeseed oil, soy oil,palms oil, and alike, and animal fats like tallow oil. The saturatedfatty acids are, caprylic acid (8:0), capric acid (10:0), lauric acid(12:0), myristic acid (14:0), palmitic acid (16:0), stearic acid (18:0),arachidic acid (20:0), behenic acid (22:0), lignoceric acid (24:0), orcerotic acid(26:0).

In another embodiment of the present invention is represented by anisomerized structural formula (VI-a):

or a mixture of structural isomers.wherein R is a C₁-C₂₆ linear or branched alkyl chain or a saturatedfatty acid or saturated fatty acids derived from renewable resourceslike plant oils like Jatropha, vegetable oils like canola oil, palm oil,vegetable oils like canola, rapeseed oil, soy oil, palms oil, and alike,and animal fats like tallow oil. The saturated fatty acids are, caprylicacid (8:0), capric acid (10:0), lauric acid (12:0), myristic acid(14:0), palmitic acid (16:0), stearic acid (18:0), arachidic acid(20:0), behenic acid (22:0), lignoceric acid (24:0), or ceroticacid(26:0), and the remaining variables are as described in theimmediately preceding paragraph or for structural formula (I), (II) or(III).

In another embodiment, the present invention addresses to a compoundrepresented by structural formula VII

whereinR is an alkenyl isomer represented by

or a mixture of structural isomers,R^(d) is H or a C₁-C₁₈ linear or branched alkyl chain, —[CH₂]_(p)—CH₃with p being an integer from 0 to 30. In some instances p is from 3 to25, in some instances p is 7 to 17, in some instances p is from to 17,in some instances p from 13-15, in some instances p is from 15 to 17, insome instances p is 0, 7, 9, 11, 13, 15, or 17 or a mixture thereof.

Each R₁ is H, independently an optionally substituted C₁-C₂₀ linear orbranched alkyl group, a tertiary carbon group, a methyl group, a methoxygroup, an optionally substituted aryl group, and an optionallysubstituted C₁-C₂₀ linear or branched alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted C₁-C₂₀ linear orbranched alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH) whereineach R′″ independently is C₁-C₁₀ linear or branched alkyl chain, —OH,—SH or —NH₂ or an optionally substituted carbocyclic or heterocyclicC₁-C₁₂ non-aromatic ring.

i=0 or 1,j=0 or 1;n is an integer from 0 to 100 or 0 to 50 or 0 to 25, 0 to 15, orpreferably 0 to 10;when n=1, then j is always 0;when n>1 then j=1;each R₂, R₃, independently is H, methyl, or a C₁-C₈ linear or branchedor cyclic alkyl chain.

In another embodiment, the present invention is a compound of structuralformula (VII) where R₁ is an isomerized structure represented by

or a mixture of isomers.

In another embodiment, the present invention addresses to a compoundrepresented by structural formula VIII:

wherein,R is an alkenyl isomer represented by

or a mixture of isomerized structures;R^(d) is H or C₁-C₁₈ linear or branched alkyl chains, —[CH₂]_(p)—CH₃with p being an integer from 0 to 30. In some instances p is from 3 to25, in some instances p is 7 to 17, in some instances p is from to 17,in some instances p from 13-15, in some instances p is from 15 to 17, insome instances p is 0, 7, 9, 11, 13, 15, or 17 or a mixture thereof.

Each R₁ is H, independently an optionally substituted C₁-C₂₀ alkylgroup, a tertiary carbon group, a methyl group, a methoxy group, anoptionally substituted aryl group, and optionally substituted C₁-C₂₀alkoxy group, an optionally substituted carbonyl group, an optionallysubstituted C₁-C₂₀ alkoxycarbonyl group, an optionally-CH(R′″)(R′″COOH)wherein each R′″ independently is C₁-C₁₀ linear or branched alkyl chain,—OH, —SH or —NH₂ or an optionally substituted carbocyclic orheterocyclic C₁-C₁₂ non-aromatic ring;

i=0 or 1 or 2 or 3;

In another embodiment, the present invention is a compound of structuralformula VIII where R₁ is selected from the group consisting of

and,in proviso substituted phenol is not a phenol, 2,4-dimethylphenol orresorcinol if R is arising from DDSA (dodecenyl succinic anhydride),ODSA (octadecenyl succinic anhydride), OSA (octenyl succinic anhydride),or PIBSA (polyisobutylene succinic anhydride).

In another embodiment, the present invention is a compound of structuralformula (VIII) where R₁ is an isomerized structure represented by

or a mixture of isomers.

In yet another embodiment of the present invention is a compound or amixture of compounds represented by structural formulas VIII where is Ris an alkenyl portion of [monosaturated fatty acid succinic anhydride]isomers when their anhydride rings are opened by a saturated fattyalcohol selected from the chain lengths ranging from C₈ to C₂₆. Thepreferred monosaturated fatty acid-succinic anhydride is an oleicacid-succinic anhydride (OASA). The isomer structures of an OASA areconsisting of

In yet another embodiment of the present invention is a compound or amixture of compounds represented by structural formulas VIII where is Ris an alkenyl portion of [monosaturated fatty acid-succinic anhydride]isomers when their anhydride rings are opened by a fatty alcoholselected from the chain lengths ranging from C₈ to C₂₆. The preferredmonosaturated fatty acid-succinic anhydride compound is oleicacid-succinic anhydride (OASA) and the fatty acid alcohol is stearylalcohol (CH₃(CH₂)₁₇OH). The isomer structures of OASA after reactingwith a fatty alcohol, R^(d)—OH are:

wherein, R^(d) is H or C₁-C₁₈ linear or branched alkyl chains,—[CH₂]_(p)—CH₃ with p being an integer from 0 to 30. In some instances pis from 3 to 25, in some instances p is 7 to 17, in some instances p isfrom 11 to 17, in some instances p from 13-15, in some instances p isfrom 15 to 17, in some instances p is 0, 7, 9, 11, 13, 15, or 17 or amixture thereof.

In yet another embodiment, the present invention is a compound or amixture of compounds represented by structural formulas IX:

wherein R is an alkenyl structural isomer represented by

or a mixture of isomers;R_(d) is H or C₁-C₁₈ linear or branched alkyl chains, —[CH₂]_(p)—CH₃with p being an integer from 0 to 30. In some instances p is from 3 to25, in some instances p is 7 to 17, in some instances p is from to 17,in some instances p from 13-15, in some instances p is from 15 to 17, insome instances p is 0, 7, 9, 11, 13, 15, or 17 or a mixture thereof.

In yet another embodiment, the present invention is a compound or amixture of compounds represented by structural formulas X:

wherein R is an alkenyl structural isomer represented by

or a mixture isomer structures,wherein R^(d) is H or C₁-C₁₈ linear or branched alkyl chains,—[CH₂]_(p)—CH₃ with p being an integer from 0 to 30. In some instances pis from 3 to 25, in some instances p is 7 to 17, in some instances p isfrom 11 to 17, in some instances p from 13-15, in some instances p isfrom 15 to 17, in some instances p is 0, 7, 9, 11, 13, 15, or 17 or amixture thereof.

In certain embodiments, the present invention relates to a compoundrepresented by structural formula XI (a mixture of structural isomers):

or a mixture of isomers,wherein,R is a C₁-C₁₈ linear or branched alkyl chain, or an alkenyl chain ofPIBSA, OSA, DDSA, and ODSA, and the remaining variables are as describedfor structural formula (I), (II) or (III).

In yet another embodiment, the present invention is a compound or amixture of compounds represented by Structural formula XI wherein thepolymers that are the reaction products of a substituted phenol and analdehyde which is further esterified with PIBSA, DDSA, ODSA, or OSA.

In another embodiment, the present invention is a compound of isomerizedstructural formula (XI) where R₁ is represented by

or a mixture of isomers.

In yet another embodiment, the present invention is a compoundrepresented by structural formulas XII with optionally theircorresponding structural isomer or mixture of structural isomers:

wherein,OSA′, DDSA′, ODSA′, PIBSA′ are alkenyl chain portion of OSA, octenylsuccinic anhydride; DDSA, dodecenyl succinic anhydride; ODSA,octadecenyl succinic anhydride; PIBSA, polyisobutylene succinicanhydride (low molecular weight, 300-1500 molecular weight),respectively;each R₂, R₃ is independently an optionally a methyl group or H;independently an optionally a C₁-C₈ linear, branched, a cyclic alkylgroup, the remaining variables are as described for structural formula(I), (II) or (III).

In another embodiment, the present invention is a compound of structuralformula (XII) where R₁ is represented by

or a mixture of structural isomers.

In yet another embodiment, the present invention is a compoundrepresented by structural formula I where n is 1, j is 0,

-   -   wherein [X] is

-   -   R is an isomerized alkenyl chain represented by

-   -   or a mixture of isomers; and    -   each R^(d) is a C₁-C₂₄ alkyl chain.

In another embodiment of the present invention is an isomeric compoundrepresented by structural formula XIII wherein, R is an isomerizedalkenyl chain represented by

-   -   or their isomer mixtures (1)-(8); and    -   each R^(d) is a C₁-C₂₄ alkyl chain.

In another embodiment of the present invention is an isomeric compoundrepresented by structural formula XIII-A:

or a mixture of structural isomerswhereinEach R₅, R₆ independently is H, methyl, or a C₁-C₂₄ linear or branchedor cyclic alkyl chain,Each n, n′ independently is 1 to 15, preferably 4 to 10.

In another embodiment of the present invention, a method of producing acompound having Structural Formula I:

-   -   wherein    -   X is

-   -   each R₁ is H, independently an optionally substituted C₁-C₂₀        alkyl group, an optionally substituted C₁-C₁₀ alkyl group, a        tertiary carbon group, a methyl group, a methoxy group, an        optionally substituted aryl group, and optionally substituted        alkoxy group, an optionally substituted carbonyl group, an        optionally substituted alkoxycarbonyl group, an        optionally-CH(R′″)(R′″COOH) wherein each R′″ independently        C₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an        optionally substituted carbocyclic or heterocyclic non-aromatic        ring.    -   I=0, 1, 2, 3;    -   j=0 or 1;    -   n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25,        1 to 15, or preferably 1 to 10,    -   when n=1, then j=0;    -   when n>1 then j=1;    -   each R₂ and R₃ is independently H, a C1-C8 linear or branched or        cyclic alkyl chain, an optionally substituted C₁-C₂₀ alkyl        group, an optionally substituted C₁-C₁₀ alkyl group, a tertiary        carbon group, a methyl group, a methoxy group, an optionally        substituted aryl group, and optionally substituted alkoxy group,        an optionally substituted carbonyl group, an optionally        substituted alkoxycarbonyl group, or —CH(R′″)(R′″COOH)    -   R is a C₁-C₂₄ linear or branched alkyl chain, alkenyl chain, or        an isomerized structure or a mixture of isomerized (A) and (B):

-   -   wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain,    -   the method comprising:        -   (a) reacting X in a solvent with an aldehyde selected from            the group of formaldehyde, acetaldehyde, valeraldehyde,            butyraldehyde, isovalrealdehyde, 2-methyl butanal,            benzaldehyde, cyclohexanecarbaldehyde,            3-methylcyclohexanecrabaldehyde, glyceraldehyde, glucose            aldehyde,        -   (b) Reacting the product in (a) with an alkyl acyl chloride,            an oleoyl chloride, or alkenyl succinic anhydride selected            from the group of octenyl succinic anhydride (OSA),            dodecenyl succinic anhydride (DDSA); octadecenyl succinic            anhydride (ODSA); polyisobutylene succinic anhydride (PIBSA)            having a molecular weight from 300 to 1500;        -   (c) Reacting the product of (b) with maleic anhydride if the            reactant used in (b) is an oleoyl chloride, and then            finally,        -   (d) Reacting the The succinic anhydride group of product            in (c) is reacting with a C₁-C₂₄ linear or branched or            cyclic alcohol.

If the reactant used in (b) is not oleoyl chloride, then (c) can includereacting the product of (b) with oleic acid.

In certain embodiments the methods of present invention, a polymer thatis a reaction product of starting materials comprising a substitutedphenol and an aldehyde that is further esterified with an alkyl acidthrough the use of oxalyl chloride or thionyl chloride.

In certain embodiments the alklyl acid used in the methods of thepresent invention is selected from the group consisting of an alkyl withat least about 4 carbon atoms, preferably C₅ to C₂₆ acid such assaturated straight chain fatty acid including caprylic acid (8:0),capric acid (10:0), lauric acid (12:0), myristic acid (14:0), palmiticacid (16:0), stearic acid (18:0), arachidic acid (20:0), behenic acid(22:0), lignoceric acid (24:0), or cerotic acid(26:0).

In certain embodiments the substituted phenol used in the methods of thepresent invention is selected from the group consisting the structuralformulas XIV shown below:

In certain embodiments, the aldehyde used in the methods of the presentinvention is selected from the group consisting of formaldehyde,acetaldehyde, valeraldehyde, butyraldehyde, isovalrealdehyde, 2-methylbutanal, benzaldehyde, cyclohexanecarbaldehyde,3-methylcyclohexanecrabaldehyde, glyceraldehyde, glucose aldehyde.

In certain embodiments, the methods of the present invention are theproduct above referred as a substituted phenol-aldehyde polymer. Thefollowing scheme (Scheme I-A) illustrate the particular embodiments ofthis method

wherein, a substituted phenol is selected from Structural formula XIV,aldehyde is selected from formaldehyde, acetaldehyde, valeraldehyde,butyraldehyde, isovalrealdehyde, 2-methyl butanal, benzaldehyde,cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde,glyceraldehyde, glucose aldehyde; all of the remaining variables are asdescribed above or Structural formula III, n is an integer from 1 to1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15, or preferably 0 to 10,all of the remaining variables are as described above or Structuralformula II.

It is understood the use of phrase ‘substituted phenol-aldehyde polymer’refers to the product in Scheme IA.

In yet another embodiment, in the method involves adding concentratedsulfuric acid to the reaction mixture of a substituted phenol and analdehyde in distilled water and keep at the ice-bath temperature.

In yet another embodiment, in the reaction of a substituted phenol andan aldehyde, the ratio of a substituted phenol to a suitable solvent is1:1-10, 1:1-5, 1:1-3, 1:2 or 1:1 by volume. In another embodiment, inthe method above involves refluxing the reaction mixture under inertatmosphere between 1-48 hours, between 3 and 9 hours, between 6 and 12hours, or between 12 and 36 hours.

In another embodiment, in the above method involves cooling the reactionmixture to room temperature and separating the product and washing withwater.

In yet another embodiment, the reaction solvent for the mixture of asubstituted phenol and an aldehyde is selected from toluene, xylene, 1,2-dichloroethane, tetrachloroethylene, dioxane or methylethyl ketone atreflux temperature under inert atmosphere.

In another embodiment, in the above method, an acid added to thereaction mixture of a substituted phenol and an aldehyde in abovesolvents is selected from hydrochloric acid, p-toluenesulfonic acid, oroxalic acid, solid based acids, phosphoric acid and acetic acid.

In yet another embodiment, in the above method involves reacting alkylchloride to the above (substituted phenol-aldehyde) product in asuitable solvent first at ice bath temperature and then bring it to theroom temperature while stirring the reaction mixtures for 1 to 48 hours,3 to 12 hours, or 6 to 24 hours.

In yet another embodiment, in the above method involves adding triethylamine to the reaction mixture.

In yet another embodiment, in the above method involves, the alkyl acidchloride with carbons in the alkyl chain ranging from C₁ to C₂₆.Preferred alkyl acid chlorides are, C₈, C₁₂, C₁₄, C₁₆, or C₁₈ linear orbranched carbon alkyl acid chlorides.

In other embodiments, the methods of the present invention, when thesolvent is used it can be recycled by separting the solvents from thereaction mixture using distillation.

The following schemes illustrate particular embodiments of this method:

wherein, substituted phenols selected from Structural formula XIV,aldehyde is selected from formaldehyde, acetaldehyde, valeraldehyde,butyraldehyde, isovalrealdehyde, 2-methyl butanal, benzaldehyde,cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde,glyceraldehyde, glucose aldehyde; all of the remaining variables are asdescribed above or Structural formula III; n is an integer from 1 to1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15, or preferably 0 to 10.

In yet another embodiment the present invention is a method of producinga compound in Scheme I

wherein, R is a linear or branched alkyl C₁-C₂₆ chain, an alkyl C₁₂ oran alkyl C₁₆ or an alkyl C₁₈ or a mixture of alkyl C₁₂, C₁₄, C₁₆ and C₁₈chains; n is an integer from 1 to 1000 or 0 to 100, 0 to or 0 to 25, 0to 15, or preferably 0 to 10, all of the remaining variables are asdescribed above or Structural formula II.

In yet another embodiment the present invention is a method of producinga compound in Scheme II:

wherein an aldehyde is selected from a group of formaldehyde,acetaldehyde, valeraldehyde, butyraldehyde, isovalrealdehyde, or2-methyl butanal, benzaldehyde; preferably formaldehyde or acetaldehyde;wherein, R is a linear or branched alkyl C₁-C₂₆ chain, an alkyl C₁₂ oran alkyl C₁₆ or an alkyl C₁₈ or a mixture of alkyl C₁₂, C₁₄, C₁₆ and C₁₈chains; n is an integer from 1 to or 0 to 100, 0 to 50 or 0 to 25, 0 to15, or preferably 0 to 10.

In yet another embodiment the present invention is a method of producinga compound in Scheme III:

wherein, R is a linear or branched alkyl C₁-C₂₆ chain, an alkyl C₁₂ oran alkyl C₁₆ or an alkyl Cis or a mixture of alkyl C₁₂, C₁₄, C₁₆ and C₁₈chains; n is an integer from 1 to 1000 or 0 to 100, 0 to or 0 to 25, 0to 15, or preferably 0 to 10, all of the remaining variables are asdescribed above or Structural formula II.

In yet another embodiment the present invention is a method of producinga compound in Scheme IV where in a substituted phenol is selected fromStructural formula XIV.

In another embodiment, the present invention is a method of producing acompound in Scheme IV wherein a substituted phenol is selected fromStructural formula XIV.

In another embodiment the present invention is a method of producing acompound in Scheme V wherein a substituted phenol is a phenol,ortho-cresol or a mixture of ortho, meta, para-cresols, oro-methoxyphenol, and R is a linear alkyl C12 or a C16 or C18 or amixture of alkyl C₁₂, C₁₄, C₁₆ and C₁₈ chains, and n is an integer from1 to 1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15, or preferably 0 to10.

In another embodiment the present invention is a process of producing acompound in Structural Formulas IV:

wherein n is an integer from 0 to 100 or 0 to 50 or 0 to 25, 0 to 15, orpreferably 0 to 10

In certain embodiments of this invention relates to a macromolecularcorrosion inhibitor that is a polymer which is the reaction product ofthe starting materials comprising a substituted phenol and an aldehydeand is further reacted with an alkenyl succinic anhydride to form anisomerized half ester product having a free carboxylic acid group in therepeating unit.

In another embodiment, the substituted phenol is selected from theStructural formulas XIV and an aldehyde is selected from formaldehyde,acetaldehyde, valeraldehyde, butyraldehyde, isovalrealdehyde, 2-methylbutanal, benzaldehyde, cyclohexanecarbaldehyde,3-methylcyclohexanecrabaldehyde, glyceraldehyde, glucose aldehyde.

In one embodiment, an alkenyl succinic anhydride is selected from thegroup consisting of DDSA, ODSA, OSA, PIBSA form an isomerized half esterproduct having free carboxylic acid groups in the alkenyl chain of therepeating group.

In yet another embodiment the present invention is a method of producingan isomerized compound in Scheme VI:

wherein an alkenyl succinic anhydride is selected from the groupconsisting of DDSA, ODSA, OSA, PIBSA to form an isomerized half esterproduct having free carboxylic acid groups in the alkenyl chain of therepeating group, and n is an integer from 1 to 1000 or 0 to 100, 0 to 50or 0 to 25, 0 to 15, or preferably 0 to 10 and all of the remainingvariable are as described above or Structural formula XI and remainingvariables are as described for structural formula II.

In yet another embodiment the present invention is a method of producinga compound with a mixture of isomers (A) and (B) in Scheme VI.

In yet another embodiment the present invention is a method of producinga compound with mixture of isomerized (A) and (B) in Structural formulasXII

wherein OSA′, DDSA′, ODSA′, PIBSA′ are alkenyl chain portion of OSA,octenyl succinic anhydride; DDSA, dodecenyl succinic anhydride; ODSA,octadecenyl succinic anhydride; PIBSA, polyisobutylene succinicanhydride (low molecular weight, 300-1500 molecular weight),respectively; and n is an integer from 1 to 1000 or 0 to 100, 0 to 50 or0 to 25, 0 to 15, or preferably 0 to 10, and all of the remainingvariables are as described above or Structural formula II.

In another embodiment the present invention is a method of producing acompound with mixture of isomers (A) and (B) in Structural formulas XIIwherein the mixture of a substituted phenol-aldehyde polymer reactedwith an alkenyl succinic anhydride selected from the group consisting ofDDSA, dodecenyl succinic anhydride; ODSA, octadecenyl succinicanhydride; PIBSA, polyisobutylene succinic anhydride (low molecularweight, 300-1500 molecular weight) reaction temperatures between 80° C.to 175° C. between 1 and 24 hours, between 3 to 12 hours, or between6-24 hours.

In yet another embodiment the present invention is a method of producinga compound with mixture of isomers (A) and (B) in Structural formulasXII wherein a substituted phenols is selected from Structural formulasXIV and an aldehyde is selected from an aldehyde is selected fromformaldehyde, acetaldehyde, valeraldehyde, butyraldehyde,isovalrealdehyde, 2-methyl butanal, benzaldehyde,cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde,glyceraldehyde, glucose aldehyde.

In yet another embodiment the present invention is a method of producinga compound with a mixture of isomers (A) and (B) in Structural formulasXII wherein an aldehyde is formaldehyde or acetaldehyde.

In yet another embodiment the present invention is a method of producinga compound with a mixture of isomerized structures in Structuralformulas XII.

In yet another embodiment of this invention relates to a macromolecularcorrosion inhibitor that is a polymer which is the reaction product ofthe starting materials comprising a substituted phenol and an aldehydeare further reacted with an alkylene oxide (e.g. propylene oxide) toform a phenol-derived alcohol in the repeating unit and is furtherreacted with an alkyl acid. Generally, Fischer esterification of aphenol with an alkyl acid is not an efficient one. However, the reactionis efficient if the phenolic-OH is converted to an alkyl alcohol and isfurther reacted with a linear or branched C₁-C₂₆ alkyl acid. Thesubstituted phenol is selected from the structural formulas (XIV) and analdehyde is selected from formaldehyde, acetaldehyde, valeraldehyde,butyraldehyde, isovalrealdehyde, 2-methyl butanal, benzaldehyde,cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde,glyceraldehyde, glucose aldehyde.

In certain embodiments, the methods of the present invention to producea compound that includes the esterification of a substitutedphenol-aldehyde polymer (Schemes I-A, VII-A) by reacting with an oleoylchloride followed by reacting with maleic anhydride and finally reactedwith an alkyl alcohol to form an isomerized alkenyl chain continuinghalf acid ester groups (Scheme VII-I).

In one embodiment of the method of producing a compound with substitutedphenol group consisting of a substituted phenol is selected fromStructural formula XIV; and an aldehyde is selected from formaldehyde,acetaldehyde, valeraldehyde, butyraldehyde, isovalrealdehyde, 2-methylbutanal, benzaldehyde, cyclohexanecarbaldehyde,3-methylcyclohexanecrabaldehyde, glyceraldehyde, glucose aldehyde; allof the remaining variables are as described above or Structural formulaIII.

In certain embodiments of the present invention is a method of producingan isomerized compound is represented by

-   -   wherein,    -   R is a C₁-C₂₄ linear or branched alkyl chain, an isomerized        alkenyl chain or a mixture of isomerized alkenyl chains        represented by

-   -   wherein R^(d) is a linear or branched C₁-C₂₄ alkyl chain; or    -   an isomerized structure or a mixture of isomerized (A) and (B)

-   -   wherein R^(a) is a C₁-C₂₄ linear or branched alkenyl chain, an        alkenyl chain portion of OSA, octenyl succinic anhydride; DDSA,        dodecenyl succinic anhydride; ODSA, octadecenyl succinic        anhydride; PIBSA, polyisobutylene succinic anhydride (low        molecular weight, 300-1500 molecular weight, and    -   R₁ is selected from the group consisting of

-   -   n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25,        1 to 15, or preferably to 10,    -   a method comprising:    -   (a) Reacting in a solvent at reflux a phenol having the        following formula:

(wherein R₁ is selected from the group consisting of

-   -   an isomerized alkyl acid chain or a mixture of isomerized alkyl        acid chains as shown below

-   -   with    -   formaldehyde,    -   (b) The product in (a) is reacting with an oleoyl chloride or        alkyl acyl chloride at ice temperature to room temperature for 1        hour to 24 hours, or an alkenyl succinic anhydride is selected        from the group of OSA, octenyl succinic anhydride; DDSA,        dodecenyl succinic anhydride; ODSA, octadecenyl succinic        anhydride; PIBSA, polyisobutylene succinic anhydride (low        molecular weight, 300-1500 molecular weight) at 80° C. to        150° C. for 1 to 24 hours,    -   (c) The product in (b) is reacting with maleic anhydride at 170°        C.-210° C. for 1 hour to hours if the reactant used in (b) is an        oleoyl chloride, and then finally    -   (d) The succinic anhydride group of product in (c) is reacting        with a C₁-C₂₄ linear or branched or cyclic alcohol at 80° C. to        150° C., if the reactant used in (b) is an oleoyl chloride.

In yet another embodiment the present invention is a method of producingan isomerized compound in Scheme VII:

wherein variables are described for structural formula III, and R^(d) isan isomerized alkenyl chain, and n is an integer from 1 to 1000 or 0 to100, 0 to 50 or 0 to 25, 0 to 15, or preferably 0 to 10,

wherein R^(g) is an isomerized oleate succinic anhydride chain (SchemeVII-I),R^(d) is an isomerized oleate half-acid ester chain.

In yet another embodiment the present invention is a method of producingan isomerized compound in Scheme VIII:

wherein R^(g) is an isomerized oleate succinic anhydride chain (SchemeVII-I), R^(d) is an isomerized oleate half-acid ester, and n is aninteger from 1 to 1000 or 0 to 100, 0 to 50 or 0 to 25, 0 to 15, orpreferably 0 to 10.

In yet another embodiment the present invention is a method of producingan isomerized compound in Scheme IX:

wherein R^(g) is an isomerized oleate succinic anhydride chain (SchemeVII-I), R^(d) is an isomerized oleate half-acid ester chain; n is aninteger from 1 to 1000 or 0 to 100, 0 to or 0 to 25, 0 to 15, orpreferably 0 to 10.

In one embodiment of the present invention is directed to forming apolymer by reacting a substituted phenol with a formaldehyde followed bypost esterification of the reaction with oleoyl chloride is furtherreacted with maleic anhydride at reaction temperatures between 170° C.and 210° C. between 1 and 24 hours, between 3 to 12 hours, or between6-24 hours.

In yet another embodiment, in the above method, the molar ratio of thereaction product (of a substituted phenol with formaldehyde followed bypost esterification of the reaction with oleoyl chloride) and maleicanhydride is 1:0.8, 1:0.9, 1:1.0, or 1:2.

In yet another embodiment, in the above method, a suitable solvent isselected from the group consisting of toluene, xylene, chlorobenzene,dimethyl formamide, dimethyl sulfoxide, 1, 2-dichlorobenzene,dimethylsuccinate, diisobutyl adipate and diisobutyl glutarate.

In yet another embodiment, in the above method, the weight ratio of asolvent and the reaction product (a substituted phenols reacted withformaldehyde followed by post esterification of the reaction with oleoylchloride further reacted with maleic anhydride) is 0.1 to 1.0:1.0

In yet another embodiment, in the above method involves distilling thesolvent from the reaction mixture.

In one embodiment of the present invention is directed to forming apolymer by reacting the reaction product (a substituted phenols reactedwith formaldehyde followed by post esterification of the reaction witholeoyl chloride further reacted with maleic anhydride) is furtherreacted with an alkyl alcohol to form half acid ester selected from thegroup consisting of linear or branched C₁-C₂₄ chain at reactiontemperatures between 80° C. and 150° C. between 1 and 24 hours, between3 to 12 hours, or between 6-24 hours.

In another embodiment of the present invention is a method of producinga mixture of isomerized compounds in Scheme X:

wherein each R₅, R^(d) independently is a linear or branched C₁-C₂₄alkyl chain.

In certain embodiments of the present invention the compounds are in thesalt forms to improve the solubility in certain fluids; for example,water or fluid mixtures, for example, metal working fluids, water basedor oil based paints.

In another embodiment the present invention is a method of producing amixture of the isomerized compounds in Scheme XII:

wherein R^(d) is an C₁-C₂₄ alcohol.In another embodiment of the present invention is a method of making acompound having the following structure with a mixture of isomericstructures:

wherein [X] is

R is an isomerized alkenyl chain represented by

wherein R^(d) independently is a linear or branched C₁-C₂₄ alkyl chain,the method comprising:

-   -   a. reacting in a solvent or in bulk an oleic acid with a C₁-C₂₄        linear or branched or cyclic alcohol,    -   b. the product in (a) is reacting with a maleic anhydride at        170° C.-210° C. for 1 hour to hours, and finally    -   c. the succinic anhydride group of product in (b) is reacting        with an X at 80° C. to 150 CC.

As used here, the terms “lubricants” and “lubricant oils” can be usedinterchangeably. Examples of lubricants suitable for use in thecompositions and methods of the present invention include, but are notlimited to: i) petroleum based oils (Group I, II and III), ii) syntheticoils (Group IV, V) and iii) biolubricant oils (vegetable oils such ascanola, soybean, high oleic canola, high oleic soybean oil, corn oil,castor oil, jatropha, etc.). Group I oils, as defined herein are solventrefined base oils. Group II oils, as defined herein are modernconventional base oils made by hydrocracking and early waxisomerization, or hydroisomerization technologies and have significantlylower levels of impurities than Group I oils. Group III oils, as definedherein are unconventional base oils. Groups I-III differ in impurities,and viscosity index as is shown in Kramer et al. “The Evolution of BaseOil Technology” Turbine Lubrication in the 21^(st) Century ASTM STP#1407 W. R. Herguth and T. M. Wayne, Eds., American Society for Testingand Materials, West Conshohocken, Pa., 2001 the entire contents of whichare incorporated herein by reference. Group IV oils as defined hereinare “synthetic” lubricant oils, including, for example, poly-alphaolefins (PAOs). Biolubricants, as defined herein, are lubricants whichcontain at least 51% biomaterial (see Scott Fields, Environmental HealthPerspectives, volume 111, number 12, September 2003, the entire contentsof which are incorporated herein by reference). Other examples oflubricant oils can be found in Melvyn F. Askew “Biolubricants-MarketData Sheet” IENICA, August 2004 (as part of the IENICA work stream ofthe IENICA-INFORRM project); Taylor et al. “Engine lubricant TrendsSince 1990” paper accepted for publication in the Proceedings I. Mech.E. Part J, Journal of Engineering Tribology, 2005 (Vol. 219 p 1-16); andDesplanches et al. “Formulating Tomorrow's Lubricants” page 49-52 of ThePaths to Sustainable Development, part of special report published inOctober 2003 by Total; the entire contents of each of which areincorporated herein by reference. Biolubricants are often but notnecessarily, based on vegetable oils. Vegetable derived, for example,from rapeseed, sunflower, palm, and coconut can be used asbiolubricants. They can also be synthetic esters which may be partlyderived from renewable resources. They can be made from a wider varietyof natural sources including solid fats and low grade or waste materialssuch as tallows. Biolubricants in general offer rapid biodegradabilityand low environmental toxicity.

As used herein, Group I, II and III oils are petroleum base stock oil.The petroleum industry differentiates their oil based on viscosity indexand groups them as Group I, II and III. The synthetic oils are Group IVand Group V. Synthetic oils include hydrocarbon oil. Hydrocarbon oilsinclude oils such as polymerized and interpolymerized olefins(polybutylenes, polypropylenes, propylene isobutylene copolymers,ethylene-olefin copolymers, and ethylene-alpha olefin copolymers, forexample). Poly alpha olefin (PAO) oil base stocks are commonly usedsynthetic hydrocarbon oil. By way of example, PAOs derived from C₈, C₁₀,C₁₂, C₁₄ olefins or mixtures thereof may be utilized. In certainembodiments, PAO is a bio-based oil. In certain embodiments, syntheticoils are polyolesters for example diesters, polyolesters such asneopentyl glycols (NPGs), trimethylolpropanes (TMPs), penterythritols(PEs), and dipentaerythritols (DiPEs). In other embodiments, syntheticoils include monoesters and trimellitates. In other embodiments,synthetic oils include polyalkylene glycols (PAGs). In general,synthetic esters described herein are obtained by reacting one or morepolyhydric alcohols with alkyl acids. Polyhydric alcohols preferablyinclude the hindered polyols (such as the neopentyl polyols, e.g.,neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol,trimethylol propane, pentaerythritol, and dipentaerythritol) and alkylacids include least about 4 carbon atoms, preferably C₅ to C₂₆ acidssuch as saturated straight chain fatty acids including caprylic acid,capric acid, lauric acid, myristic acid, palmitic acid, stearic acid,arachic acid, and behenic acid, or the corresponding branched chainfatty acids or unsaturated fatty acids such as oleic acid, or mixturesof any of these materials.

In certain embodiments of the present invention, mixtures of synthetic(Groups IV and V) and bio-oils or petroleum based oils (Groups I, II,III) and biooils, or petroleum based oils and synthetic oils, ormixtures of bio-oils, synthetic oils and petroleum base oils may beused.

In certain embodiments of the present invention, 0.001% to 10% by weightof the corrosion inhibitors of the present invention is added tolubricant oils. In certain other embodiments of the present invention,10% to 5% by weight of the corrosion inhibitors of the present inventionare added to lubricant oils. In certain other embodiments of the presentinvention, 0.001% to 2% by weight of the corrosion inhibitors of thepresent invention is added to lubricant oils. In certain otherembodiments of the present invention, 0.001% to 0.5% by weight of thecorrosion inhibitors of the present invention is added to lubricantoils. This percentage varies depending upon their end application andtype of the base oil.

In certain embodiments of the present invention, the corrosioninhibitors of the present invention are usually added to lubricant oilswith stirring at between 0 and 100° C., between 20 and 80° C. or between40-60° C.

In certain embodiments of the present invention, the corrosioninhibitors of the present invention are usually added to lubricant andfuel oils (based on petroleum, synthetic, and/or bio-based oils)(examples, gasoline, diesel, biodiesel (B10, B20, up to B100 wherenumbers after letter B corresponds to percentage of fatty acid methylesters (FAME) content in diesel) used in automotives, and industrialapplications such as but not limited to transmission fluid, engine oil,break oil, metal working fluids, greases, gear oils, hydraulic fluids,transformer oils, elevator oils wire and rope oils, drilling oils,turbine oils used for hydro-power turbines, aviation turbines, windturbines, metal working fluids, etc.

In certain embodiments, the mixture of corrosion inhibitors of thepresent invention is preferred due to improved solubilitycharacteristics as compared to a single component corrosion inhibitor.

In yet other embodiments of the present invention of corrosioninhibitors have significantly improved solubility characteristics inpetroleum (Group I-V oils), bio-based oils and bio-oils. This is mainlyattributed to the design of the molecules of the current inventioncontaining alkyl chains to increase the solubility.

In certain embodiments of the present invention of corrosion inhibitors,The key innovative aspects of products include:

-   -   1. Macromolecular product design, which improves efficiency by        forming more effective molecular barrier films on metal        surfaces. These barriers are responsible for inhibiting        corrosion, thereby, maintaining superior performance with        intelligent molecular design.    -   2. Free from all inorganic species. No species such as Zn, Pb,        Sn, P, Cr, Si, B, S, As, etc.    -   3. Environmentally friendly. Low aquatic toxicity, better        biodegradability, and low/no bioaccumulation.    -   4. Produced with bio-based, renewable raw materials to the        maximum extent possible (˜85.0%)

In certain embodiments of the present invention of corrosion inhibitorsis preferred due to multifunctional characteristics to protect againstrust corrosion, copper, aluminum and alloy corrosion and also waterseparability from oil (as a demulsifier). In general three independentadditives each one proving desired rust inhibition, copper protection,and demulsifiers are used in the formulation. The present inventionprovides all three protections by a single compound. This significantlyreduces the number of additives required in the lubricant formulation atleast from three additives to one single additive providing rustinhibition, copper protection against corrosion and performs as ademulsifier to separate water from oil. It is economically attractive byreducing three additives to one for the lubricant formulation.

In certain embodiments of the present invention are the most suitablefor environmentally acceptable lubricants because of their low aquatoxicity to fish, daphnia, and algae.

In certain embodiments of the present invention of corrosion inhibitorsis preferred in aftermarket automotive lubricant products.

In certain embodiments of the present invention of corrosion inhibitorshave excellent solubility in bio-oils, bio-based oils, synthetic oils,petroleum based oils.

In yet other embodiments of the present invention, the corrosioninhibitors of the present invention are usually added to lubricant andfuel oils along with other additional lubricant additives including butnot limited to antioxidants, anti-foaming, a viscosity modifier, pourpoint depressants, and other phenolic and aminic antioxidants.

In one embodiment, the present invention is a composition comprisingpresent invention corrosion inhibitors, and at least one additiveselected from the group consisting of i) a surface additive; ii) aperformance enhancing additive, and iii) a lubricant protectiveadditive.

In another embodiments the present invention is a lubricant compositioncomprising: a lubricant or a mixture of lubricants, a present inventioncorrosion inhibitor and at least one additive selected from the groupconsisting of i) a surface additive; ii) a performance enhancingadditive, and iii) a lubricant protective additive.

In yet another embodiment the present invention is a method of improvinga composition comprising combining the composition with presentinvention corrosion inhibitor, and at least one additive selected fromthe group consisting of i) a surface additive; ii) a performanceenhancing additive, and iii) a lubricant protective additive.

In yet another embodiment the present invention is a method of improvinga lubricant or a mixture of lubricants comprising combining thelubricant or mixture of lubricants with present invention corrosioninhibitor, and at least one additive selected from the group consistingof i) a surface additive; ii) a performance enhancing additive; and iii)a lubricant protective additive.

The compositions and methods of the present invention generally provideincreased shelf life, increased oxidative resistance, enhancedperformance and/or improved quality to materials, such as, for example,lubricants and lubricant oils and fuels. Other examples include.biolubricants and biolubricant oils and biofuel such as biodiesel. Ingeneral, it is believed that because of the synergy of the corrosioninhibitors with the additives, the compositions described herein havesuperior corrosion resistance. The additives exhibit several keyfunctions such as corrosion inhibition, detergency, viscositymodification, and antiwear performance, dispersant properties, cleaningand suspending ability. The disclosed compositions, in general, providesuperior performance of lubricants in high temperatures applications dueto the presence of high performance additives which are thermally stableat high temperatures with enhanced oxidation resistance.

In yet another embodiment the present invention of corrosion inhibitorsis suitable for other corrodible materials including but not limited tofuels, biofuel, diesel, biodiesel, aviation fuels, kerosene, etc.

In certain embodiments, the present invention of corrosion inhibitors issuitable for additive packages for lubricants and fuels. These packagesare for aftermarket products to enhance the performance of lubricantsand fuel. Other additive packages designed for formulating lubricantsand fuel by adding to base stock oils; petroleum based (Group I-V oils),bio-based, bio-oils, and gasoline, diesel, and biodiesel.

In one embodiment, the present invention is an additive packagecomposition comprising present invention corrosion inhibitors, and atleast one additive selected from the group consisting of i) a surfaceadditive; ii) a performance enhancing additive, and iii) a lubricantprotective additive.

In another embodiments the present invention is an additive packagecomposition comprising: a lubricant or a mixture of lubricants, apresent invention corrosion inhibitor and at least one additive selectedfrom the group consisting of i) a surface additive; ii) a performanceenhancing additive, and iii) a lubricant protective additive.

In yet another embodiment the present invention is a method of improvingan additive package composition comprising combining the compositionwith present invention corrosion inhibitor; and at least one additiveselected from the group consisting of i) a surface additive; ii) aperformance enhancing additive, and iii) a lubricant protectiveadditive.

In yet another embodiment the present invention is a method of improvingan additive package composition comprising combining the compositionwith present invention corrosion inhibitor comprising additives one ormore of an antioxidant, a metal deactivator, rust inhibitor, coppercorrosion inhibitor, viscosity index modifier, pour point depressant,dispersing agent, detergent, an extreme-pressure, a dye, seal swellagents, a demulsifiers, and an anti-foaming additive; each additivepresent in the range 0.005%-5% and a carrier oil. A suitable carrierfrom petroleum, biobased, bio-oil is the one that dissolves alladditives and easy to pour into a lubricant or a fuel. The ratio betweenadditives and carrier oil may range from 1:99 to 99:1 by weight %, 5:95by weight %, 10:90 by weight %, 20:90 by weight %, 30:70 by weight %,40:60 by weight %, 50:50 by weight %, 60:40 by weight %, 70:30 by weight%, 80:20 by weight %, 90:10 by weight %, 95:5 by weight %.

In yet another embodiment the present invention of corrosion inhibitorsmay typically apply to coatings and paints including multi-packagesystems which are usually mixed prior to use, the pigments, catalystsand other additives can be added.

In yet another embodiment the present invention applications includebase coat and clear coat formulations especially in the automotive,aviation, and marine industry.

Stabilized Lubricant Oil Compositions

Lubricants, lubricant oils, mixtures thereof and compositions comprisinglubricants and lubricant oils can be improved by the methods of thepresent invention, by contacting the lubricant, lubricant oil, mixturesthereof or composition comprising the lubricant or lubricant oil ormixtures thereof with corrosion inhibitors, additives and mixturesthereof as described herein.

As used here, the terms “lubricants” and “lubricant oils” can be usedinterchangeably. Examples of lubricants suitable for use in thecompositions and methods of the present invention include, but are notlimited to: i) petroleum based oils (Group I, II and III), ii) syntheticoils (Group IV and V)) and iii) biolubricant oils (vegetable oils suchas canola, soybean, corn oil etc.), and bio-based oils like polyolesters, biobased esters like estolides, bio-poly alpha olefins, bioalkylene glycols, bio poly alkylene glycols. Group I oils, as definedherein are solvent refined base oils. Group II oils, as defined hereinare modern conventional base oils made by hydrocracking and early waxisomerization, or hydroisomerization technologies and have significantlylower levels of impurities than Group I oils. Group III oils, as definedherein are unconventional base oils. Groups I-III differ in impurities,and viscosity index as is shown in Kramer et al. “The Evolution of BaseOil Technology” Turbine Lubrication in the 21^(st) Century ASTM STP#1407 W. R. Herguth and T. M. Wayne, Eds., American Society for Testingand Materials, West Conshohocken, Pa., 2001 the entire contents of whichare incorporated herein by reference. Group IV oils as defined hereinare “synthetic” lubricant oils, including, for example, poly-alphaolefins (PAOs). Biolubricants, as defined herein, are lubricants whichcontain at least 51% biomaterial (see Scott Fields, Environmental HealthPerspectives, volume 111, number 12, September 2003, the entire contentsof which are incorporated herein by reference). Other examples oflubricant oils can be found in Melvyn F. Askew “Biolubricants-MarketData Sheet” IENICA, August 2004 (as part of the IENICA work stream ofthe IENICA-INFORRM project); Taylor et al. “Engine lubricant TrendsSince 1990” paper accepted for publication in the Proceedings I. Mech.E. Part J, Journal of Engineering Tribology, 2005 (Vol. 219 p 1-16); andDesplanches et al. “Formulating Tomorrow's Lubricants” page 49-52 of ThePaths to Sustainable Development, part of special report published inOctober 2003 by Total; the entire contents of each of which areincorporated herein by reference. Biolubricants are often but notnecessarily, based on vegetable oils. Vegetable derived, for example,from rapeseed, sunflower, palm, and coconut can be used asbiolubricants. They can also be synthetic esters which may be partlyderived from renewable resources. They can be made from a wider varietyof natural sources including solid fats and low grade or waste materialssuch as tallows. Biolubricants in general offer rapid biodegradabilityand low environmental toxicity.

Additives

Examples of first additives suitable for use in the compositions andmethods of the present invention include but are not limited to, surfaceadditives, performance enhancing additives and lubricant protectiveadditives.

Surface additives: In certain embodiments of the present invention,surface additives can protect the surfaces that are lubricated fromwear, corrosion, rust, and frictions. Examples of these surfaceadditives suitable for use in the compositions and methods of thepresent invention include, but are not limited to: (a) rust inhibitors,(b) corrosion inhibitors, (c) extreme pressure agents, (d) tackinessagents, (e) antiwear agents, (f) detergents and dispersants, (g)compounded oil (like fat or vegetable oil to reduce the coefficient offriction without affecting the viscosity), (h) antimisting, (i) sealswelling agents and (j) biocides.

Performance Enhancing Additives: In certain embodiments of the presentinvention, performance enhancing additives improve the performance oflubricants. Examples of these performance enhancing additives suitablefor use in the Compositions and methods of the present inventioninclude, but are not limited to: (a) pour-point depressants, (b)viscosity index modifiers (c) emulsifiers, and (d) demulsifiers.

Lubricant Protective Additives: In certain embodiments of the presentinvention, lubricant protective additives maintain the quality of oilfrom oxidation and other thermal degradation processes. Examples ofthese lubricant protective additives suitable for use in thecompositions and methods of the present invention include, but are notlimited to: (a) oxidation inhibitors and (b) foam inhibitors.

Other Lubricant Additives

In certain embodiments, a second additive can be used in thecompositions and methods of the present invention in combination withthe first antioxidant and the first additive as described above.Examples of second additives suitable for use in the compositions andmethods of the present invention include, include but are not limitedto, for example, dispersants, detergents, corrosion inhibitors, rustinhibitors, metal deactivators, antiwear and extreme pressure agents,antifoam agents, friction modifiers, seal swell agents, demulsifiers,viscosity index improvers, pour point depressants, and the like. See,for example, U.S. Pat. No. 5,498,809 for a description of usefullubricating oil composition additives, the disclosure of which isincorporated herein by reference in its entirety.

Dispersants: Examples of dispersants suitable for use in thecompositions and methods of the present invention include, but are notlimited to polybutenylsuccinic acid-amides, -imides, or -esters,polybutenylphosphonic acid derivatives, Mannich Base ashlessdispersants, and the like.

Detergents: Examples of detergents suitable for use in the compositionsand methods of the present invention include, but are not limited tometallic phenolates, metallic sulfonates, metallic salicylates, metallicphosphonates, metallic thiophosphonates, metallic thiopyrophosphonates,and the like.

Corrosion Inhibitors: Examples of corrosion inhibitors suitable for usein the compositions and methods of the present invention include, butare not limited to: phosphosulfurized hydrocarbons and their reactionproducts with an alkaline earth metal oxide or hydroxide,hydrocarbyl-thio-substituted derivatives of 1,3,4-thiadiazole,thiadiazole polysulphides and their derivatives and polymers thereof,thio and polythio sulphenamides of thiadiazoles such as those describedin U.K. Patent Specification 1,560,830, and the like.

Rust Inhibitors: Examples of rust inhibitors suitable for use in thecompositions and methods of the present invention include, but are notlimited to: nonionic surfactants such as polyoxyalkylene polyols andesters thereof, anionic surfactants such as salts of alkyl sulfonicacids, and other compounds such as alkoxylated fatty amines, amides,alcohols and the like, including alkoxylated fatty acid derivativestreated with C9 to C16 alkyl-substituted phenols (such as the mono- anddi-heptyl, octyl, nonyl, decyl, undecyl, dodecyl and tridecyl phenols).

Metal Deactivators: Metal deactivators as used herein, are the additiveswhich form an inactive film on metal surfaces by complexing withmetallic ions and reducing, for example, the catalytic effect on metalgum formation and other oxidation. Examples of metal deactivatorssuitable for use in the compositions and methods of the presentinvention include, but are not limited to N, N-disubstitutedaminomethyl-1, 2, 4-triazoles, N, N-disubstitutedaminomethyl-benzotriazoles, mixtures thereof, and the like.

Antiwear and Extreme Pressure Additives: Antiwear and extreme pressureadditives, as used herein, react with metal surfaces to form a layerwith lower shear strength then metal, thereby preventing metal to metalcontact and reducing friction and wear. Examples of antiwear additivessuitable for use in the compositions and methods of the presentinvention include, but are not limited to: sulfurized olefins,sulfurized esters, sulfurized animal and vegetable oils, phosphateesters, organophosphites, dialkyl alkylphosphonates, acid phosphates,zinc dialkyldithiophosphates, zinc diaryldithiophosphates, organicdithiophosphates, organic phosphorothiolates, organic thiophosphates,organic dithiocarbamates, dimercaptothiadiazole derivatives,mercaptobenzothiazole derivatives, amine phosphates, aminethiophosphates, amine dithiophosphates, organic borates, chlorinatedparaffins, and the like.

Antifoam Agents: Examples of antifoam agents suitable for use in thecompositions and methods of the present invention include, but are notlimited to: polysiloxanes and the like.

Friction Modifiers: Examples of friction modifiers suitable for use inthe compositions and methods of the present invention include, but arenot limited to: fatty acid esters and amides, organic molybdenumcompounds, molybdenum dialkylthiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiolates, copper oleate, coppersalicylate, copper dialkyldithiophosphates, molybdenum disulfide,graphite, polytetrafluoroethylene, and the like.

Seal Swell Agents: Seal swell agents, as used herein, react chemicallywith elastomers to cause slight swell thus improving low temperatureperformance especially in, for example, aircraft hydraulic oil. Examplesof seal swell agents suitable for use in the compositions and methods ofthe present invention include, but are not limited to: dioctyl sebacate,dioctyl adipate, dialkyl phthalates, and the like.

Demulsifiers: Demulsifiers, as used herein promote separation of oil andwater in lubricants exposed to water. Examples of demulsifiers suitablefor use in the compositions and methods of the present inventioninclude, but are not limited to: the esters described in U.S. Pat. Nos.3,098,827 and 2,674,619 incorporated herein by reference.

Viscosity Index Improvers: Examples of viscosity index improverssuitable for use in the compositions and methods of the presentinvention include, but are not limited to olefin copolymers, dispersantolefin copolymers, polymethacrylates,vinylpyrrolidone/methacrylate-copolymers, polyvinylpyrrolidones,polybutanes, styrene/-acrylate-copolymers, polyethers, and the like.

Pour Point Depressants: Pour point depressants as used herein reduce thesize and cohesiveness of crystal structure resulting in low pour pointand increased flow at low-temperatures. Examples of pour pointdepressants suitable for use in the compositions and methods of thepresent invention include, but are not limited to: polymethacrylates,alkylated naphthalene derivatives, and the like.

Other Antioxidants and Stabilizers

In certain embodiments, a second antioxidant or a stabilizer can be usedin the compositions and methods of the present invention in combinationwith the first antioxidant and the first additive and optionally thesecond additive as described above. Examples of second antioxidantssuitable for use in the compositions and methods of the presentinvention include, include but are not limited to:

-   1. Amine Antioxidants-   1.1. Alkylated Diphenylamines, for example octylated diphenylamine;    styrenated diphenylamine; mixtures of mono- and dialkylated    tert-butyl-tert-octyldiphenylamines; and 4,4′-dicumyldiphenylamine.-   1.2. Phenyl Naphthylamines, for example N-phenyl-1-naphthylamine;    N-phenyl-2-naphthylamine; tert-octylated N-phenyl-1-naphthylamine.-   1.3. Derivatives of para-Phenylenediamine, for example    N,N′-diisopropyl-p-phenylenediamine;    N,N′-di-sec-butyl-p-phenylenediamine;    N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine;    N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;    N,N′-bis(1-methylheptyl)-p-phenylenediamine;    N,N′-diphenyl-p-phenylenediamine;    N,N′-di-(naphthyl-2)-p-phenylenediamine;    N-isopropyl-N′-phenyl-p-phenylenediamine;    N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine;    N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine;    N-cyclohexyl-N′-phenyl-p-phenylenediamine;    N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine.-   1.4. Phenothiazines, for example phenothiazine;    2-methylphenothiazine; 3-octylphenothiazine;    2,8-dimethylphenothiazine; 3,7-dimethylphenothiazine;    3,7-diethylphenothiazine; 3,7-dibutylphenothiazine;    3,7-dioctylphenothiazine; 2,8-dioctylphenothiazine.-   1.5. Dihydroquinolines, for example    2,2,4-trimethyl-1,2-dihydroquinoline or a polymer thereof.-   2. Phenolic Antioxidants-   2.1. Alkylated monophenols, for example    2,6-di-tert-butyl-4-methylphenol; 2,6-di-tert-butylphenol;    2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol;    2,6-di-tert-butyl-4-n-butylphenol;    2,6-di-tert-butyl-4-isobutylphenol;    2,6-di-tert-butyl-4-sec-butylphenol;    2,6-di-tert-butyl-4-octadecylphenol;    2,6-di-tert-butyl-4-nonylphenol; 2,6-dicyclopentyl-4-methylphenol;    2-(β-methylcyclohexyl)-4,6-dimethylphenol;    2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;    2,6-di-tert-butyl-4-methoxymethylphenol;    2,6-di-tert-butyl-4-dimethylaminomethylphenol; o-tert-butylphenol.-   2.2. Alkylated hydroquinones, for example    2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone;    2,5-di-tert-amylhydroquinone; 2,6-di-phenyl-4-octadecyloxyphenol.-   2.3. Hydroxylated thiodiphenyl ethers, for example    2,2′-thiobis(6-tert-butyl-4-methyl-phenol);    2,2′-thiobis(4-octylphenol);    4,4′-thiobis(6-tert-butyl-3-methylphenol);    4,4′-thiobis(6-tert-butyl-2-methylphenol).-   2.4. Alkylidenebisphenols, for example    2,2′-methylenebis(6-tert-butyl-4-methylphenol);    2,2′-methylenebis(6-tert-butyl-4-ethylphenol);    2,2′-methylenebis(4-methyl-6-(α-methylcyclohexyl)phenol);    2,2′-methylenebis(4-methyl-6-cyclohexylphenol);    2,2′-methylenebis(6-nonyl-4-methylphenol);    2,2′-methylenebis(4,6-di-tert-butylphenol);    2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol);    2,2′-methylenebis[6-□-methylbenzyl)-4-nonylphenol];    2,2′-methylenebis[6-(α, α-dimethylbenzyl)-4-nonylphenol];    4,4′-methylenebis(2,6-di-tert-butylphenol);    4,4′-methylenebis(6-tert-butyl-2-methylphenol);    1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;    2,6-di(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;    1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;    ethylene glycol    bis[3,3-bis(3′-tert-butyl-4′-hydroxylphenyl)butyrate];    di(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;    di[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate.-   2.5. Benzyl compounds, for example    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;    di(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide;    3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester;    bis(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl)dithioterephthalate;    1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;    1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate;    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester;    3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid mono-ethyl ester    calcium salt.-   2.6. Acylaminophenols, for example 4-hydroxylauric acid anilide;    4-hydroxystearic acid anilide;    2,4-bis-octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyaniline)-s-triazine;    N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamic acid octyl ester.-   2.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid    with mono- or polyhydric alcohols, e.g. with methanol; octadecanol;    1,6-hexanediol; neopentyl glycol; thiodiethylene glycol; diethylene    glycol; triethylene glycol; pentaerythritol;    tris(hydroxyethyl)isocyanurate; and di(hydroxyethyl)oxalic acid    diamide.-   2.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic    acid with mono- or polyhydric alcohols, e.g. with methanol;    octadecanol; 1,6-hexanediol; neopentyl glycol; thiodiethylene    glycol; diethylene glycol; triethylene glycol; pentaerythritol;    tris(hydroxyethyl)isocyanurate; and di(hydroxyethyl)oxalic acid    diamide.-   2.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid,    e.g.,    N,N′-di(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hexamethylenediamine;    N,N′-di(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine;    N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.-   3. Sulfurized organic compounds, for example aromatic, alkyl, or    alkenyl sulfides and polysulfines; sulfurized olefins; sulfurized    fatty acid esters; sulfurized ester olefins; sulfurized oils; esters    of β-thiodipropionic acid; sulfurized Diels-Alder adducts;    sulfurized terpene compounds; and mixtures thereof.-   4. Organo-borate compounds, for example alkyl- and aryl- (and mixed    alkyl, aryl) substituted borates.-   5. Phosphite and phosphate antioxidants, for example alkyl- and    aryl- (and mixed alkyl, aryl) substituted phosphites, and alkyl- and    aryl- (and mixed alkyl, aryl) substituted dithiophosphates such as    O,O,S-trialkyl dithiophosphates, O,O,S-triaryldithiophosphates and    dithiophosphates having mixed substitution by alkyl and aryl groups,    phosphorothionyl sulfide, phosphorus-containing silane,    polyphenylene sulfide, amine salts of phosphinic acid and quinone    phosphates.-   6. Copper compounds, for example copper dihydrocarbyl thio- or    dithiophosphates, copper salts of synthetic or natural carboxylic    acids, copper salts of alkenyl carboxylic acids or anhydrides such    as succinic acids or anhydrides, copper dithiocarbamates, copper    sulphonates, phenates, and acetylacetonates. The copper may be in    cuprous (Cu^(I)) or cupric (Cu^(II)) form.-   7. Zinc dithiodiphosphates, for example zinc    dialkyldithiophosphates, diphenyldialkyldithiophosphates, and    di(alkylphenyl)dithiophosphates.

In one embodiment, the compositions for use in the methods of thepresent invention, include but are not limited to:

a. a first corrosion inhibitor (in the concentration range, from about0.0001% to about 50%, from about 0.0005% to about 20%, from about 0.005%to about 10%, from about 0.05% to about 5% or from about 0.01% to about1%) with a first additive selected from the group comprising anantioxidant, a surface additive, a performance enhancing additive and alubricant performance additive, for example, in amounts of from about0.0005% to about 50%, from about 0.0001% to about 20%, from about 0.005%to about 10%, from about 0.05% to about 5% or from about 0.01% to about1% by weight, based on the weight of lubricant to be stabilized.

b. the first corrosion inhibitor and the first additive as described ina. and a second additive, for example, in concentrations of from about0.0001% to about 50% by weight, about 0.0005% to about 20% by weight,about 0.001% to about 10% by weight, from about 0.01% to about 5% byweight, from about 0.05% to about 1% by weight from about 0.1% to about1% by weight based on the overall weight of the lubricant to bestabilized.

c. the first corrosion inhibitor and the first additive as described ina. and optionally the second additive as described in b. and a secondcorrosion inhibitor, for example, Irgacor® 190, Irgacor® NPA, Cuvan®303, Cuvan® 484, Cuvan® 826, in the concentration range, from about0.0001% to about 50%, from about 0.0005% to about 20%, from about 0.005%to about 10%, from about 0.05% to about 5% or from about 0.01% to about1%) by weight, based on the weight of lubricant to be stabilized.

In yet another embodiment, the antioxidant compositions for use in themethods of the present invention include but is not limited to: thefirst antioxidant from the present invention and the second antioxidantfrom the section.

‘Other Antioxidants and Stabilizers’.

The antioxidant composition, where in the weight ratio of the secondantioxidant to the first antioxidant of the present invention is fromabout 1:99 to 99:1, from about 10:90, 20:80, 30:70, 40:60, 50:50, 60:40,70:30, 80:20, 90:10. The second antioxidant second antioxidant, forexample, Irganox® L 57, Irganox® L64, Irganox® 1330, Irganox® 1076,Irganox® 5057 and Irganox L 135, Polnox®7030, Polnox® 7070, Polnox®8020, Polnox®8060, Polnox®8080.

Example 1

Octanoyl chloride (1 mL, 5.82 mmol) was added slowly to the mixture of2-t-butyl-4-methoxyphenol (1 g, 5.82 mmol) and triethylamine (0.81 mL,5.82 mmol) dissolved in THF in ice-bath under a nitrogen atmosphere. Thereaction mixture was stirred overnight at room temperature undernitrogen atmosphere. The completion of the reaction was confirmed by TLCand FTIR. The mixture was filtered to remove salt and then washed withTHF. It was then concentrated under reduced pressure. The crude productwas dissolved in EtOAc and extracted with saturated NaHCO₃ and brine.The organic phase was dried over anhydrous Na₂SO₄. Concentration invacuo gave the target compounds as a light yellow liquid.

Example 2

The same method in Example 1 is used with a linear alkyl chain of C₁₂,C₁₆ and C₁₈ atoms and a branched alkyl chain with C₈ atoms.

Example 3

The same method in Example 1 is used for the synthesis of phenol andsubstituted phenols such as 2-methoxyphenol, o-cresol, m-cresol,p-cresol and o, m, p-cresol mixtures, 2-sec-butylphenol,2-tert-amylphenol, 2-tert-butylphenol, 2-isopropyl-5-methylphenol,eugenol, isoeugenol, 4-ethyl-2-methoxyphenol, 4-t-butylphenol,resorcinol, catechol, and phloroglucinol.

Example 4

The same method in Example 1 is used with a linear alkyl chain of C₁₂,C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms for phenol andsubstituted phenols in Example 3.

Example 5

Oxalyl chloride (6 mL, 67.06 mmol) was added slowly to the mixture ofo-cresol (5.74 g, 53.12 mmol) and stearic acid (15.11 g, 53.12 mmol) indichloromethane (15 mL) with a catalytic amount (a couple of drops) ofDMF in ice-bath under a nitrogen atmosphere. The reaction mixture wasstirred for 30 min at this temperature under nitrogen atmosphere. Then,the reaction mixture was stirred at 60° C. for 6-10 h. The completion ofthe reaction was confirmed by TLC and FTIR. After cooling, the crudeproduct was extracted with saturated NaHCO₃ and brine. The organic phasewas dried over anhydrous Na₂SO₄. It was then concentrated under reducedpressure. Concentration in vacuo gave the target compound.

Example 6

The same method in Example 5 is used with a linear alkyl chain of C₁₂,C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms.

Example 7

Example 5 is synthesized using thionyl chloride instead of oxalylchloride.

Example 8

The same method in Example is used with a linear alkyl chain of C₁₂, C₁₆and C₁₈ atoms and a branched alkyl chain of C₈ atoms for phenol andsubstituted phenols such as 2-methoxyphenol, 2-t-butyl-4-methoxyphenol,m-cresol, p-cresol and o,m,p-cresol mixtures, 2-sec-butylphenol,2-tert-amylphenol, 2-tert-butylphenol, 2-isopropyl-5-methylphenol,eugenol, isoeugenol, 4-ethyl-2-methoxyphenol, 4-t-butylphenol,resorcinol, catechol and phloroglucinol.

Example 9

The same method in Example 7 is used with a linear alkyl chain of C₁₂,C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms for phenol andsubstituted phenols such as 2-methoxyphenol, 2-t-butyl-4-methoxyphenol,m-cresol, p-cresol and o,m,p-cresol mixtures, 2-sec-butylphenol,2-tert-amylphenol, 2-tert-butylphenol, 2-isopropyl-5-methylphenol,eugenol, isoeugenol, 4-ethyl-2-methoxyphenol, 4-t-butylphenol,resorcinol, catechol and phloroglucinol.

Example 10

Concentrated H₂SO₄ (161.2 mL, 3 mol) was added slowly to a reactionmixture of 2-methoxyphenol (150 g, 1.21 mol) and formaldehyde (37% aq)(90.8 mL, 1.21 mol) in distilled water (600 mL) in ice-bath. Then, thereaction mixture was refluxed under N₂ for 6-10 h. The completion of thereaction was confirmed by TLC. After cooling down the reaction mixture,solution phase was decantated and the precipitate was washed with water.The precipitate dried under vacuum gave the target product as lightyellow to brown powder. This reaction was done using other solvents suchas toluene and 1,2-dichloroethane. This reaction was also done usingoxalic acid as a catalyst.

Example 11

The same method in Example 10 was used for the synthesis of o-cresol,o,m,p-cresol mixtures, 2-t-butyl-4-methoxyphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, and 4-t-butylphenol. It is also used otherssuch as m-cresol, p-cresol, 2-sec-butylphenol, 2-tert-amylphenol,2-tert-butylphenol, 2-isopropyl-5-methylphenol, resorcinol, catechol,and phloroglucinol. This reaction was done using other solvents such astoluene and 1,2-dichloroethane. This reaction was done using oxalic acidas a catalyst.

Example 12

Lauroyl chloride (152 mL, 0.639 mol) in 300 mL of THF was added slowlyto the mixture of the product from Example 10 (100 g, 0.188 mol) andtriethylamine (88.5 mL, 0.639 mol) dissolved in 600 mL of THF inice-bath under a nitrogen atmosphere. The reaction mixture was stirredovernight at room temperature under nitrogen atmosphere. The completionof the reaction was confirmed by FTIR. The mixture was filtered toremove salt and then washed with THF. It was then concentrated underreduced pressure. The crude product was dissolved in EtOAc, extractedwith saturated NaHCO₃ and brine. The organic phase was dried overanhydrous Na₂SO₄. Concentration in vacuo gave the target compounds aslight yellow oil.

Example 13

The same method in Example 12 was used with a linear alkyl chain of C₈,C₁₂, C₁₆ and a branched alkyl chain of C₈ atoms. It is also used with alinear alkyl chain of C₁₈ atoms.

Example 14

The same method in Example 5 is used with a linear alkyl chain of C₈,C₁₂, C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms forExample 13.

Example 15

The same method in Example 5 is used with a linear alkyl chain of C₈,C₁₂, C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms forExample 13.

Example 16

The same method in Example 12 was used with a linear alkyl chain of C₈for 4-t-butylphenol and 2-t-butyl-4-methoxyphenol used as startingmaterial in Example 11. The same method in Example 5 is used with alinear alkyl chain of C₈, C₁₂, C₁₆ and C₁₈ atoms and a branched alkylchain of C₈ atoms for the other compounds obtained in Example 11.

Example 17

The same method in Example 5 is used with a linear alkyl group of C₈,C₁₂, C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms forExample 11.

Example 18

The same method in Example 7 is used with a linear alkyl chain of C₈,C₁₂, C₁₆ and C₁₈ atoms and a branched alkyl chain of C₈ atoms forExample 11.

Example 19

Oxalyl chloride (3.7 mL, 42.56 mmol) was added slowly to the mixture of2-methoxyphenol (4.49 g, 35.47 mmol) and oleic acid (10.02 g, 35.47mmol) with a catalytic amount (a couple of drops) of DMF in ice-bathunder a nitrogen atmosphere. The reaction mixture was stirred for 30 minat this temperature under nitrogen atmosphere. Then, the reactionmixture was stirred at 60° C. for 6-10 h. The completion of the reactionwas confirmed by TLC and FTIR. After cooling, the crude product wasextracted with saturated NaHCO₃ and brine. The organic phase was driedover anhydrous Na₂SO₄. It was then concentrated under reduced pressure.Concentration in vacuo gave the target compound yellow oil. Thisreaction was done using thionyl chloride.

Example 20

The same method in Example 19 was used for phenol, o-cresol, resorcinoland catechol. It is also used others such as 2-t-butyl-4-methoxyphenol,m-cresol, p-cresol, o,m,p-cresol mixtures, 2-sec-butylphenol,2-tert-amylphenol, 2-tert-butylphenol, 2-isopropyl-5-methylphenol,eugenol, isoeugenol, 4-ethyl-2-methoxyphenol and 4-t-butylphenol, andphloroglucinol. Dichloromethane was used as a solvent of substitutedphenols which are solid at reaction temperature 60° C.

Example 21

Example 19 was synthesized using thionyl chloride instead of oxalylchloride.

Example 22

Example 20 is synthesized using thionyl chloride instead of oxalylchloride.

Example 23

Oxalyl chloride (3.6 mL, 41.3 mmol) was added slowly to the mixture ofthe product in Example (5 g, 9.39 mmol) and oleic acid (9 g, 31.9 mmol)in dichloromethane (25 mL) with a catalytic amount (0.1 mL) of DMF inice-bath under a nitrogen atmosphere. The reaction mixture was stirredfor 30 min at this temperature under nitrogen atmosphere. Then, thereaction mixture was stirred at 60° C. for 6-10 h. The completion of thereaction was confirmed FTIR. After cooling, the crude product wasextracted with saturated NaHCO₃ and brine. The organic phase was driedover anhydrous Na₂SO₄. It was then concentrated under reduced pressure.Concentration in vacuo gave the target compound as yellow oil. Thisreaction was done using thionyl chloride. This reaction was also done asfollowing: Thionyl chloride was added slowly to the mixture of an oleicacid with a catalytic amount of DMF in ice-bath by scrubbing gaseousproducts into aqueous sodium hydroxide solution. The reaction mixturewas stirred at room temperature for 2-h. Excess thionyl chloride wasdistilled of. In a separate flask, the product of Example 10 wasdissolved in 1,2-dichloroethane by followed by addition oftriethylamine. Then, this mixture was added drop wise over a period of30 min into oleoyl chloride in ice-bath under a nitrogen atmosphere. Thereaction mixture was stirred at room temperature for 8-16 h. Thecompletion of the reaction was confirmed FTIR. The salt formed in thereaction was filtered out and washed with the reaction solvent. Theconcentration of filtrate in rotavapor gave the target compound asyellow oil. This was done using other solvents such as ethyl acetate andtoluene.

Example 24

The compound in Example 23 was synthesized using thionyl chlorideinstead of oxalyl chloride.

Example 25

The same method in Example 24 was used to attach oleic acid to thecompounds obtained in Example 12 such as using o-cresol, o,m,p-cresolmixtures, resorcinol, and catechol. It is also used others such as usingm-cresol, p-cresol, 2-sec-butylphenol, 2-tert-amylphenol,2-tert-butylphenol, 2-isopropyl-5-methylphenol,2-t-butyl-4-methoxyphenol, eugenol, isoeugenol, 4-ethyl-2-methoxyphenoland 4-t-butylphenol and phloroglucinol.

Example 26

Example 25 is synthesized using thionyl chloride instead of oxalylchloride.

Example 27

Concentrated H₂SO₄ (1.9 mL, 0.036 mol) was added slowly to a reactionmixture of oleic acid (101 g, 0.36 mol) in MeOH (200 mL). Then, themixture was refluxed for 2-4 h under nitrogen atmosphere. The completionof the reaction was confirmed by FTIR. After cooling down the reactionmixture, the crude product was concentrated in vacuo. It was thenextracted with saturated NaHCO₃ and brine. The organic phase was driedover anhydrous Na₂SO₄. Concentration in vacuo gave the target product aslight yellow oil.

Example 28

The same method in Example 27 was used for the attachment of C₄ alkylchain. It is also used for the attachment of C₂ and C₃ alkyl chains.

Example 29

The mixture of oleic acid (7.51 g, 26.6 mmol), 1-octadecanol (7.19 g,26.6 mmol), PTSA.H₂O (0.51 g, 2.7 mmol) and molecular sieves werestirred at 110° C. for 4 h under a nitrogen atmosphere. The completionof the reaction was confirmed by FTIR. After cooling down the reactionmixture, molecular sieves were filtered and washed with EtOAc. Thefiltrate was then extracted with saturated NaHCO₃ and brine. The organicphase was dried over anhydrous Na₂SO₄. Concentration in vacuo gave thetarget product as a yellow wax.

Example 30

The same method in Example 29 is used for the attachment of a linearalkyl chain of C₈, C₁₂ and C₁₆ atoms and a branched alkyl chain of C₈atoms.

Example 31

Example 30 is synthesized using apparatus Dean-Stark instead ofmolecular sieves.

Example 32

The same method in Example 31 is used to make Example 30.

Example 33

To a 50 ml two-neck round bottom flask equipped thermocouple-temperaturecontroller was added methyl oleate obtained in Example 28 (25.22 g,85.08 mmol) and maleic anhydride (8.34 g, 85.08 mmol) in dimethylsuccinate (6 mL, 0.2 eq. by wt). The reaction mixture was stirred at175° C. under a nitrogen atmosphere for 4-6 h. The completion of thereaction was confirmed by FTIR and TLC. The reaction product was used innext step without further purification.

Example 34

The same method in Example 33 was used for the compounds obtained inExample 19.

Example 35

The same method in Example 33 was used for the compounds obtained inExample 20 such as using phenol, o-cresol, resorcinol, and catechol. Itis also used others such as 2-t-butyl-4-methoxyphenol, m-cresol,p-cresol, o,m,p-cresol mixtures, 2-sec-butylphenol, 2-tert-amylphenol,2-tert-butylphenol, 2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol and 4-t-butylphenol, and phloroglucinol.

Example 36

The same method in Example 33 was used for the compounds obtained inExample 23.

Example 37

The same method in Example 33 was used for the compounds obtained inExample 25 such as using o-cresol, o,m,p-cresol mixtures, resorcinol,and catechol. It is also used others such as using m-cresol, p-cresol,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, 2-t-butyl-4-methoxyphenol, eugenol,isoeugenol, 4-ethyl-2-methoxyphenol and 4-t-butylphenol andphloroglucinol.

Example 38

The same method in Example 33 was used for the compound obtained inExample 28. It is also used for the attachment of C₂ and C₃ alkylchains.

Example 39

The same method in Example 33 was used for the compound obtained inExample 29.

Example 40

The same method in Example 33 is used for the compounds obtained inExample 30.

Example 41

Propylene oxide (4.45 mL, 63.76 mmol) was added slowly to a reactionmixture of phenol (5 g, 53.13 mmol) dissolved in aqueous NaOH (4.25 g,106.2 mmol) in 15 mL water. Then, the temperature was raised to 75° C.for 16 h under nitrogen atmosphere. The completion of the reaction wasconfirmed by TLC and FTIR. After cooling down the reaction mixture, thecrude product was acidified with 1M HCl. It was diluted with EtOAc andthen extracted with saturated NaHCO₃, 1M NaOH (aq) and brine. Theorganic phase was dried over anhydrous Na₂SO₄. Concentration in vacuogave the target product as a colorless liquid.

Example 42

The same method in Example 41 is used for the substituted phenols suchas 2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresolmixtures, 2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol andphloroglucinol.

Example 43

The same method in Example 41 is used for the compound obtained inExample 10.

Example 44

The same method in Example 41 is used for the compounds obtained inExample 11.

Example 45

Octadecyl oleate succinic anhydride obtained in Example 36 (2.03 g, 2.57mmol) was stirred with 1-octadecanol (0.69 g, 2.57 mmol) and dimethylsuccinate (0.2 eq by weight) at 130° C. for 2-4 h under nitrogenatmosphere. The completion of the reaction was confirmed by FTIR. Nowork-up was required. The product appeared as yellow wax upon cooling.

Example 46

The same method in Example 45 is used for the compound obtained inExample 33 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms, ethylene glycol, hexanediol,neopentyl glycol, 2-methoxyphenol, o-cresol, m-cresol, p-cresol ando,m,p-cresol mixtures, diethanolamine, trimethylolpropane, glycerol,triethanolamine, pentaeryrthritol and di-pentaeryrthritol.

Example 47

The same method in Example 45 is used for the compound obtained inExample 34 with the reaction of C₁-C₂₄ mono alkyl alcohols, ethyleneglycol, 2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresolmixtures, hexanediol, neopentyl glycol, diethanolamine,trimethylolpropane, glycerol, triethanolamine, pentaeryrthritol, anddi-pentaeryrthritol.

Example 48

The same method in Example 45 was used for the compound obtained inExample 35 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms, 2-methoxyphenol, o-cresol, m-cresol,p-cresol and o,m,p-cresol mixtures, ethylene glycol, hexanediol,neopentyl glycol, diethanolamine, trimethylolpropane, glycerol,triethanolamine, pentaeryrthritol and di-pentaeryrthritol.

Example 49

The same method in Example 45 was used for the compound obtained inExample 36 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms.

Example 50

The same method in Example 45 was used for the compound obtained inExample 37 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms.

Example 51

The same method in Example 45 was used for the compound obtained inExample 39 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms, 2-methoxyphenol, o-cresol, m-cresol,p-cresol and o,m,p-cresol mixtures, ethylene glycol, hexanediol,neopentyl glycol, diethanolamine, trimethylolpropane, glycerol,triethanolamine, pentaeryrthritol and di-pentaeryrthritol.

Example 52

The same method in Example 45 is used for the compound obtained inExample 40 with a linear alkyl alcohol of C₈, C₁₂ and C₁₆ atoms and abranched alkyl alcohol of C₈ atoms, 2-methoxyphenol, o-cresol, m-cresol,p-cresol and o,m,p-cresol mixtures, ethylene glycol, hexanediol,neopentyl glycol, diethanolamine, trimethylolpropane, glycerol,triethanolamine, pentaeryrthritol and di-pentaeryrthritol.

Example 53

The same method in Example 45 is used the compound obtained in Example10 to react with succinic anhydrides such as a DDSA, ODSA, OSA, andPIBSA.

Example 54

The same method in Example 45 is used the compound obtained in Example11 to react with succinic anhydrides such as DDSA, ODSA, OSA, and PIBSA.

Example 55

The same method in Example 45 is used substituted phenols such as2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresol mixtures,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol andphloroglucinol to react with succinic anhydrides such as a linear alkyland a branched alkyl of octenyl succinic anhydride, tetradecenylsuccinicanhydride, hexadecenylsuccinic anhydride and polyisobutylene succinicanhydride.

Example 56

The same method in Example 45 is used substituted phenols such as2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresol mixtures,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol, andphloroglucinol to react with the compound obtained in Example 33.

Example 57

The same method in Example 45 is used substituted phenols such as2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresol mixtures,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol, andphloroglucinol to react with the compound obtained in Example 38.

Example 58

The same method in Example 45 is used substituted phenols such as2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresol mixtures,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol, andphloroglucinol to react with the compound obtained in Example 39.

Example 59

The same method in Example 45 is used substituted phenols such as2-methoxyphenol, o-cresol, m-cresol, p-cresol and o,m,p-cresol mixtures,2-sec-butylphenol, 2-tert-amylphenol, 2-tert-butylphenol,2-isopropyl-5-methylphenol, eugenol, isoeugenol,4-ethyl-2-methoxyphenol, 4-t-butylphenol, resorcinol, catechol, andphloroglucinol to react with the compound obtained in Example 40.

Example 60

The same method in Example 45 was used the compound obtained in Example41 to react with an octadecenylsuccinic anhydride.

Example 61

The same method in Example 45 is used the compound obtained in Example41 to react with other succinic anhydrides such as DDSA, ODSA, OSA, andPIBSA.

Example 62

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 33.

Example 63

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 34.

Example 64

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 35.

Example 65

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 36.

Example 66

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 37.

Example 67

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 38.

Example 64

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 39.

Example 68

The same method in Example 45 is used the compound obtained in Example41 to react with the compounds obtained in Example 40.

The performance of corrosion inhibitor can be evaluated using ASTM D130and ASTM D665 test methods for fluids like lubricants and fuels. ASTMD130 test method is suited to test the performance corrosion inhibitorsfor copper metals whereas ASTM D665 is of steel materials. The CopperStrip Tarnish Test assesses the relative degree of corrosivity ofpetroleum products, including aviation fuels, automotive gasoline,natural gasoline, solvents, kerosene, diesel fuel, distillate fuel oil,lubricating oil and other products. A polished copper strip is immersedin 30 mL of the sample at elevated temperature. After the test period,the strip is examined for evidence of corrosion and a classificationnumber from 1-4 is assigned based on a comparison with the ASTM CopperStrip Corrosion Standards. The most typical test run is for 3 hours @100° C. However, time and temperature can vary according to product typeand specification. Results are reported as a number followed by a letteraccording to the ASTM chart, a rating of 1a and 1b being an excellentcorrosion inhibitor and a rating of 4 is a poor performer.

The efficacy of the corrosion inhibitor of representative samples of thepresent invention was tested by adding 500 ppm in canola oil, Group IIoil and polyolester (synthetic oil, Group IV). The results aresummarized in Table 1.

Corrosion Inhibitor CORROSION INHIBITION RUST INHIBITION DEMULSIFICATION(ASTM D130) (ASTM D665-2) (ASTM D1401-12) Treat Canola Group PolyolTreat Canola Treat Group Canola Group Level Oil II Oil Ester Level OilLevel II Oil Oil II Oil Example 49 0.05% 1A 1B 1A 0.5% Pass 0.05% Pass40-40-0 40-40-0 (30) (30)

In a similar way, corrosion inhibitors of this invention were alsotested using ASTM D665 protocol. In this method, 300 ml of fluid treatedwith corrosion inhibitor and 30 ml of standard synthetic sea water aremixed thoroughly at 60° C. and a standard polished, cylindrical steelrod are immersed in the fluid for 4 hours. The rod will be examined fora pass or fail the test. If there is no sign of rust on the surface ofthe steel rod, a rating of Pass is given to the product. The products ofthis invention show no rust corrosion for steel rods in canola oil ifthey are treated with 0.4-0.5 weight % of the oil.

The ASTM D 1401 test method was used to study water separability of thepresent invention. In this method is a known amount of water and oiltreated with the demulsifier, 40 ml were poured in to a graduated jar ofa specified diameter. The sample was kept at a constant temperature (40°C.). Both oil and water were stirred using a motorized stirrer at aspecified specific rotation speed of 1500 rpm. The time taken for thetwo separate was measured in minutes, the faster the separation betteris the demulsibility. The results are quoted as ml-ml-emulsion (time,min). For example, 40-40-0 (30) means it took 30 minutes to separate thetwo with no emulsion. The sample of the present invention treated at thesame level for corrosion inhibitor. For example, canola was treated at0.5% with the sample of the present invention whereas Group II oil wastested at 0.05%.

While this invention has been particularly shown and described withreferences to preferred embodiments thereof, it will be understood bythose skilled in the art that various changes in form and details may bemade therein without departing from the scope of the inventionencompassed by the appended claims.

What is claimed is:
 1. A compound having Structural Formula I:

wherein: X is:

each R₁ is H, independently an optionally substituted C₁-C₂₀ alkylgroup, an optionally substituted C₁-C₁₀ alkyl group, a tertiary carbongroup, a methyl group, a methoxy group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independentlyC₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an optionallysubstituted carbocyclic or heterocyclic non-aromatic ring; i=0, 1, 2, 3;j=0 or 1; n is an integer from 1 to 1000, or an integer from 1 to 100,or an integer from 1 to 50, or an integer from 1 to 25, or an integerfrom 1 to 15, or preferably an integer from 1 to 10; when n=1, then j=0;when n>1 then j=1; each R₂ and R₃ is independently H, a C1-C8 linear orbranched or cyclic alkyl chain, an optionally substituted C₁-C₂₀ alkylgroup, an optionally substituted C₁-C₁₀ alkyl group, a tertiary carbongroup, a methyl group, a methoxy group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, or —CH(R′″)(R′″COOH); R is a C₁-C₂₄ linear or branched alkylchain, alkenyl chain, or an isomerized structure or a mixture ofisomerized (A) and (B):

wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain.
 2. Thecompound of claim 1, wherein: n=1; j=0; R is a mixture of isomerizedstructures of

and R^(d) is a C1-C24 linear or branched alkyl chain
 3. The compound ofclaim 1, wherein: [X] is

and the compound is represented by structural Formula II:

wherein: each R₂, R₃ independently is H, methyl, or a C₁-C₈ linear orbranched or cyclic alkyl chain, R is a C₁-C₂₄ linear or branched alkylchain, an isomerized alkenyl chain or a mixture of isomerized alkenylchains represented by:

wherein R^(d) is a linear or branched C₁-C₂₄ alkyl chain; or anisomerized structure or a mixture of isomerized (A) and (B)

wherein R^(a) is a C₁-C₂₄ linear or branched alkenyl chain, an alkenylchain portion of octenyl succinic anhydride (OSA); dodecenyl succinicanhydride (DDSA); octadecenyl succinic anhydride (ODSA); orpolyisobutylene succinic anhydride (PIBSA) having a molecular weightbetween 300 and
 1500. 4. The compound of claim 3, wherein each R₂, R₃ isH and j=1, wherein the compound structure is represented by Structuralformula III:

wherein, R₁ is selected from the group consisting of

an isomerized alkyl acid chain or a mixture of isomerized alkyl acidchains as shown below


5. The compound of claim 4, wherein i is 1 and compound is representedby Structural Formula IV


6. The compound of claim 5, wherein R₁ is H, CH₃, OCH₃, or a linear orbranched C₁-C₉ alkyl chain.
 7. The compound of claim 1 wherein, whereinn=1, j=0, is represented by the structural formula:

wherein [X] is

R is an isomerized alkenyl chain represented by

or mixtures thereof; and each R^(d) is a linear or branched C—C alkylchain
 8. The compound of claim 7, wherein, R is isomerized alkenyl chainrepresented by

or their isomer mixtures (1)-(8); and each R^(d) is a C₁-C₂₄ alkylchain.
 9. The compound of claim 7 wherein n=1, j=0, and the compound isrepresented by:

wherein R^(d) is a linear or branched C₁-C₂₄ alkyl chain; an isomerizedstructure or a mixture of isomerized (A) and (B)

wherein R^(a) is a C₁-C₂₄ linear or branched alkenyl chain, an alkenylchain portion of octenyl succinic anhydride (OSA); dodecenyl succinicanhydride (DDSA); octadecenyl succinic anhydride (ODSA); orpolyisobutylene succinic anhydride (PIBSA) having a molecular weightfrom 300 to 1500; and R₁ is selected from the group consisting of

an isomerized alkyl acid chain or a mixture of isomerized alkyl acidchains as shown below:

and wherein the substituted phenol is not phenol, 2,4-dimethyl phenol orresorcinol if R^(a) is an alkenyl chain portion of OSA, DDSA, ODSA, orPIBSA.
 10. The compound of claim 9, wherein i=1; and R₁ is H, CH₃, OCH₃,or a linear or branched C₁-C₁₂ alkyl chain.
 11. A mixture of a compoundrepresented by following structural formulas:

wherein each R₅ and R₆ is independently a H, methyl, or a C₁-C₂₄ linearor branched or cyclic alkyl chain; Each n and n′ is independently 1 to15, preferably 4 to 10; in particular, a compound containing thefollowing isomer structures:

wherein each R₅, R^(d) independently is a linear or branched C₁-C₂₄alkyl chain.
 12. A method of producing a compound having StructuralFormula I:

wherein X is

each R₁ is H, independently an optionally substituted C₁-C₂₀ alkylgroup, an optionally substituted C₁-C₁₀ alkyl group, a tertiary carbongroup, a methyl group, a methoxy group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independentlyC₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an optionallysubstituted carbocyclic or heterocyclic non-aromatic ring. I=0, 1, 2, 3;j=0 or 1; n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to25, 1 to 15, or preferably 1 to 10, when n=1, then j=0; when n>1 thenj=1; each R₂ and R₃ is independently H, a C1-C8 linear or branched orcyclic alkyl chain, an optionally substituted C₁-C₂₀ alkyl group, anoptionally substituted C₁-C₁₀ alkyl group, a tertiary carbon group, amethyl group, a methoxy group, an optionally substituted aryl group, andoptionally substituted alkoxy group, an optionally substituted carbonylgroup, an optionally substituted alkoxycarbonyl group, or—CH(R′″)(R′″COOH) R is a C₁-C₂₄ linear or branched alkyl chain, alkenylchain, or an isomerized structure or a mixture of isomerized (A) and(B):

wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain, the methodcomprising: (a) reacting X in a solvent with an aldehyde selected fromthe group of formaldehyde, acetaldehyde, valeraldehyde, butyraldehyde,isovalrealdehyde, 2-methyl butanal, benzaldehyde,cyclohexanecarbaldehyde, 3-methylcyclohexanecrabaldehyde,glyceraldehyde, glucose aldehyde, (b) Reacting the product in (a) withan alkyl acyl chloride, an oleoyl chloride, or alkenyl succinicanhydride selected from the group of octenyl succinic anhydride (OSA),dodecenyl succinic anhydride (DDSA); octadecenyl succinic anhydride(ODSA); polyisobutylene succinic anhydride (PIBSA) having a molecularweight from 300 to 1500; (c) Reacting the product of (b) with maleicanhydride if the reactant used in (b) is an oleoyl chloride, and thenfinally, (d) Reacting the succinic anhydride group of product in (c) isreacting with a C₁-C₂₄ linear or branched or cyclic alcohol.
 13. Themethod of claim 12, wherein the compound is represented by

wherein, R is a C₁-C₂₄ linear or branched alkyl chain, an isomerizedalkenyl chain or a mixture of isomerized alkenyl chains represented by

wherein R^(d) is a linear or branched C₁-C₂₄ alkyl chain; or anisomerized structure or a mixture of isomerized (A) and (B)

wherein R^(a) is a C₁-C₂₄ linear or branched alkenyl chain, an alkenylchain portion of OSA, octenyl succinic anhydride; DDSA, dodecenylsuccinic anhydride; ODSA, octadecenyl succinic anhydride; PIBSA,polyisobutylene succinic anhydride (low molecular weight, 300-1500molecular weight, and R₁ is selected from the group consisting of

n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1 to 25, 1 to 15,or preferably to 10, a method comprising: (a) Reacting in a solvent atreflux a phenol having the following formula:

wherein R₁ is selected from the group consisting of

an isomerized alkyl acid chain or a mixture of isomerized alkyl acidchains as shown below

with formaldehyde, (b) The product in (a) is reacting with an oleoylchloride or alkyl acyl chloride at ice temperature to room temperaturefor 1 hour to 24 hours, or an alkenyl succinic anhydride is selectedfrom the group of OSA, octenyl succinic anhydride; DDSA, dodecenylsuccinic anhydride; ODSA, octadecenyl succinic anhydride; PIBSA,polyisobutylene succinic anhydride (low molecular weight, 300-1500molecular weight) at 80° C. to 150° C. for 1 to 24 hours, (c) Theproduct in (b) is reacting with maleic anhydride at 170° C.-210° C. for1 hour to hours if the reactant used in (b) is an oleoyl chloride, andthen finally (d) The succinic anhydride group of product in (c) isreacting with a C₁-C₂₄ linear or branched or cyclic alcohol at 80° C. to150° C., if the reactant used in (b) is an oleoyl chloride.
 14. Themethod of claim 13 wherein a substituted phenol is selected from thegroup of

preferably phenol, ortho-cresol, a mixture of o-,m-, and p-cresol,2-methoxy phenol, or a C₁-C₁₂ linear or branched alkyl chain.
 15. Themethod of claim 14 wherein the aldehydes is formaldehyde oracetaldehyde.
 16. The method of claim 12 wherein a product comprisesstructural isomers if an alkenyl chain is attached to the substitutedphenol.
 17. A method of making a compound in claim 7 having thefollowing a mixture of isomeric structures:

wherein [X] is

R is an isomerized alkenyl chain represented by

wherein R^(d) independently is a linear or branched C₁-C₂₄ alkyl chain,the method comprising: a) reacting in a solvent or in bulk an oleic acidwith a C₁-C₂₄ linear or branched or cyclic alcohol, b) the product in(a) is reacting with a maleic anhydride at 170° C.-210° C. for 1 hour tohours, and finally c) c. the succinic anhydride group of product in (b)is reacting with an X—OH selected from a group of a substituted phenol,ethylene glycol, hexanediol, neopentyl glycol, diethanolamine,trimethylolpropane, glycerol, triethanolamine, pentaeryrthritol,di-pentaeryrthritol at 80° C. to 150° C.
 18. The method of claim 17having the following a mixture of isomeric structures:

wherein each R₅, R^(d) independently is a linear or branched C₁-C₂₄alkyl chain, the method comprising: a) reacting in a solvent or in bulkan oleic acid with a C₁-C₂₄ linear or branched or cyclic alcohol usingan acidic catalyst selected from sulfuric acid, para-toluene sulfonicacid, solid phase catalysts, and phosphoric acid. b) the product in (a)is reacting with a maleic anhydride at 170° C.-210° C. for 1 hour tohours, and finally c) the succinic anhydride group of product in (b) isreacting with a C₁-C₂₄ linear or branched or cyclic alcohol at 80° C. to150° C. for 1 to 24 hours.
 19. A method of preventing corrosion in acorrodible material, comprising combining the corrodible material with acompound represented by the following structural formula:

wherein X is

Each R₁ is H, independently an optionally substituted C₁-C₂₀ alkylgroup, an optionally substituted C₁-C₁₀ alkyl group, a tertiary carbongroup, a methyl group, a methoxy group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally-CH(R′″)(R′″COOH) wherein each R′″ independentlyC₁-C₁₀ linear or branched alkyl chain, —OH, —SH or —NH₂ or an optionallysubstituted carbocyclic or heterocyclic non-aromatic ring. i=0 or 1 or 2or 3; j=0 or 1; n is an integer from 1 to 1000 or 1 to 100, 1 to 50 or 1to 25, 1 to 15, or preferably 1 to 10, when n=1, then j=0; when n>1 thenj=1; Each R₂, R₃, is H, independently a C1-C8 linear or branched orcyclic alkyl chain, independently an optionally substituted C₁-C₂₀ alkylgroup, an optionally substituted C₁-C₁₀ alkyl group, a tertiary carbongroup, a methyl group, a methoxy group, an optionally substituted arylgroup, and optionally substituted alkoxy group, an optionallysubstituted carbonyl group, an optionally substituted alkoxycarbonylgroup, an optionally-CH(R′″)(R′″COOH) R is a C₁-C₂₄ linear or branchedalkyl chain, alkenyl chain, or an isomerized structure or a mixture ofisomerized (A) and (B):

wherein R^(a) is a C₁-C₂₄ alkenyl linear or branched chain.
 20. Themethod of claim 19 wherein the corrodible material is a bio-oil ormodified bio-oil, vegetable oil and/or animal fat, polyolesters,synthetic or bio poly alpha olefins (PAO), polyalkylene glycols (PAG),biobased esters like polyol esters and estolides, petroleum based GroupI, II, III, IV, and V oil, or mixture thereof, lubricants,biolubricants, biobased lubricants, gasoline, kerosene, diesel, grease,and biodiesel oil, hydraulic oil, turbine oil, transformer oil, elevatoroil, 2-stroke engine oil, engine oil, and water based paints, cements,metal surfaces of, iron, steel, copper, aluminum, and alloys; plastics,bioplastics, polyolefins, nylons, polyamides, elastomers, thermoplasticelastomers, natural and synthetic polymers and copolymers.
 21. Acomposition comprising: a) a compound according to claim 1; and b) abio-oil or modified bio-oil, a vegetable oil and/or animal fat, apolyolester, a synthetic or bio poly alpha olefin (PAO), a polyalkyleneglycols (PAG), a biobased ester like polyol ester and estolides, apetroleum based Group I, II, III, IV, and V oil, or mixture thereof; andc) one or more of an antioxidant, a metal deactivator, rust inhibitor,copper corrosion inhibitor, viscosity index modifier, pour pointdepressant, a dispersing agent, a detergent, an extreme-pressure, a dye,a seal swell agent, a demulsifier, or an anti-foaming additive.
 22. Thecomposition of claim 21, wherein the composition is an additive packagecomprising additives one or more of an antioxidant, a metal deactivator,rust inhibitor, copper corrosion inhibitor, viscosity index modifier,pour point depressant, dispersing agent, detergent, an extreme-pressure,a dye, a seal swell agent, a demulsifier, and an anti-foaming additive;each additive present is mixed into a carrier oil selected from a groupof petroleum, bio-based, bio-oil to formulate a fluid includinggasoline, diesel, biodiesel, a base stock oil selected from the group ofa bio-oil, a biobased oil, petroleum oil, Group I, Group II, Group III,Group IV oil, Group V or mixture thereof or to a already formulatedlubricating oil for enhancing further the fluid or lubricantperformance.
 23. A process for the inhibition of the metal corrosion dueto contact with the fluid which comprises incorporating into the fluidan effective corrosion inhibiting amount of a compound of Structure (I)of claim 1.